Coordination-polymeric triethanolamineperchlorato(triflato)metal inner complexes as additives for synthetic polymers

ABSTRACT

Stabilizer system for chlorinated polymers, especially PVC, comprising at least one coordination-polymeric triethanolamineperchlorato(triflato)metal inner complex comprising the monomer unit of the formula (A) 
     
       
         
         
             
             
         
       
     
     The stabilizer system may additionally comprise substituted cyanoacetylureas or/and 6-aminouracils or/and 3-aminocrotonic esters or/and hydantoins or/and monomeric or polymeric dihydropyridines or alkaline earth metal hydroxides or/and hydrotalcites or/and dawsonites or/and zeolites or/and glycidyl compounds or/and cyanamides or/and cyanoguanidines or/and melamines. In addition, phosphites or/and sterically hindered amines or/and NOR-HALS compounds may be present.

The present invention relates to compositions composed of syntheticpolymers and coordination-polymerictriethanolamineperchlorato(triflato)metal inner complexes, and tostabilizer systems comprising the inner complexes. The invention furtherrelates to selected inner complexes and to their preparation.

It is known that halogenated plastics or moulding materials producedtherefrom lead to degradation or decomposition reactions when they areexposed to thermal stress or come into contact with high-energyradiation, for example ultraviolet light.

To stabilize PVC, for example, before processing, heavy metalstabilizers based on Cd, Pb, Sn and Zn or toxicologically less dangerousmetals such as barium have been used to date in industry. In thesecases, the already harmful effect—with regard to improved absorbabilityand compatibility in warm-blooded organisms—is additionally increased byconversion to organic metal compounds based on fatty acids, e.g.laurates, stearates and oleates, or by virtue of transformation toorgano derivatives (organometallic compounds or metal organyls),especially in the case of tin. Specifically in the latter case, thealkylation of the metal to form a metal-carbon bond which ishydrolysis-stable even under metabolic conditions provides a gastricjuice-resistant system which is capable of overcoming the blood-brainbarrier in order to develop a possibly neurotoxic potential.

These problems affect not only the users of finished PVC articles butalso their manufacturers, which incorporate such heavy metal stabilizersin the PVC substrate. Also affected are the producers of thesestabilizers themselves, which convert heavy metal precursors toprecisely these stabilizers.

In addition to the toxic effect on warm-blooded organisms, these metalsand their (organic) compounds or organo compounds have “ecotoxicaction”, i.e. a harmful effect on fish, crabs and other seawater andfreshwater organisms; see “List of Priority Hazardous Substances” agreedat the Third North Sea Conference (The Hague, March 1990). This listincludes zinc as well as lead, cadmium, arsenic and mercury. See alsoGuideline 2000/60/EC (Determination of the List of Priority Substancesin the Field of Water Policy—last update November 2001) and the“Progress Report” of the Fifth North Sea Conference (Bergen, March2002), which states that, among others, the objective values for zincwere not met. In addition, in the sewage sludge directive of the GermanFederal Environment Office (BGB1. I p. 1492, last update 25.04. 2002),maximum amounts for heavy metals, specifically Pb, Cd, Cr, Cu, Ni, Hgand Zn, are fixed. It is also possible for inorganic heavy metal salts,through the mechanism of biomethylation present in nature, to beconverted to highly neurotoxic compounds. What should be contemplatedhere are especially trimethyllead and trimethyltin compounds. Organicstabilizers based on the elements C, H, N, O are converted in refuseincineration to CO₂, H₂O and ammonium compounds, all of which arebiocompatible. Heavy metal compounds, in contrast, are not degraded, andare thus persistent and therefore bioaccumulate.

The substitution of heavy metal stabilizers by organic compounds shouldtherefore be an important contribution to achieving this aim. In the UKand Denmark, the use of Pb stabilizers in PVC drinking water pipes wasbanned at the end of 2002 and 2003 respectively. In Denmark, this ban isadditionally combined with the requirement not to use Sn stabilizersinstead of PB stabilizers. Other countries such as Sweden, Norway andFinland wish to follow this ban. An EU-wide lead ban is currently beingnegotiated in the competent authorities.

There is thus a need for organic (“green”) stabilizers which are free ofheavy metals/heavy metal compounds or other toxicologically unsafemetals/metal compounds, and are especially free of lead, tin and barium.

Alkali metal or alkaline earth metal perchlorate salts in the presenceof metal soaps are costabilizers for flexible PVC which have been knownfor some time, especially in the motor vehicle sector, and this additiveis intended to retard PVC discoloration in backmoulded PU injectionmouldings (JP 59184240, JP 6219732, JP 03097748, U.S. Pat. No.4,957,954, EP 273766 A, JP 03126745).

Later, it was found that the addition of inorganic perchlorate saltsleads to an improvement in the efficacy of organically stabilized (heavymetal-free=Zn- and Pb-free) rigid PVC (EP 768336 A2).

A further inorganic perchlorate salt-containing stabilizer is likewiseknown from Japan. This is an anion-modified hydrotalcite. It is likewiseused principally in flexible PVC (EP 522810 A2).

Recently, two applications which describe the replacement of inorganicperchlorate salts by onium salts, specifically ammonium perchloratesalts, have been published (DE 10160662 A1, DE 10214152 A1). Two furtherapplications for uses in the PVC sector likewise come from Japan; theycomprise, inter alia, compounds including triethanolammonium (TEA)perchlorate (JP 61009451) or trialkylethanolammonium perchloratesurfactants (JP 1090242), which can find use as antistats. In addition,there exists another larger group of Japanese patents which claimtetraalkylammonium perchlorate surfactants as antistatic components inPVC. Also worthy of mention in this connection are DE 2540655A and thepublication by S. Riethmayer in Gummi, Asbest, Kunststoffe (GAK), [4],298-308 (1973).

A further modification (on an inorganic basis) of alkali metalperchlorate salts is accomplished by addition of calcium hydroxide (DE10124734 A1). This dry mixture is obtained by an “in situ” process fromaqueous perchlorate salt solution and burnt lime.

It is also known that melamine and hydantoin can be blended withperchlorate salts and these mixtures can be used as PVC thermalstabilizers (JP 53016750). However, the examples cited there usually uselarge amounts of plasticizer or immensely high proportions of calciumstearate and/or large amounts of inorganic fillers. For thestabilization of rigid PVC, though, these systems are unsuitable.

Moreover, it is known that primary alkanolamines can be complexed withzinc glutamate or sulphate. Also described in EP 394547 A2 arestabilizer systems for PVC which include liquid alkali metal or alkalineearth metal perchlorate complexes with polyols as components.N-containing polyols as complex ligands and complexes in solid form arenot claimed. It is also known that alkanolamines can be used togetherwith perchlorate salts as PVC thermal stabilizers (WO 02/48249). Solidsolutions or complexes or even inner complexes are not described there.In addition, solutions of metal perchlorate salts in glycols or glycolethers as stabilizer constituents are claimed (WO 94/24200). Inaddition, absorbates of alkali metal or alkaline earth metalperchlorates on zeolites or calcium silicate have been described manytimes before in patents, such as in EP 768336 A2 and U.S. Pat. No.5,034,443, and also in U.S. Pat. No. 5,225,108. However, these arementioned specifically as stabilizer components in EP 1404756 A1.

All of these publications are characterized by further numerousdisadvantages:

1. Virtually all inorganic perchlorate salts melt at above 250° C.,usually above 300° C., and decompose as they do so. They are thereforedifficult to disperse homogeneously in the polymer substrate anddifficult to digest. Moreover, owing to their granularity, they oftenform spots and inclusions in the finished moulded article. Fine grindingof the perchlorate salts, which might provide a remedy, istechnologically difficult to carry out.2. Inorganic perchlorate salts are in most cases hygroscopic and cake oragglomerate in the course of storage. This is shown by the fact thatmagnesium perchlorate is even used as a desiccant.3. Inorganic perchlorate salts on supports, such as calcium silicate orzeolites, are not usable universally. Transparent rigid PVC productscannot be produced with these additives.4. Aqueous solutions or solutions of these salts in an organic solventcan be used in principle, but, firstly, water in the stabilizer systemleads to incompatibility and interreaction in the polymer, and to bubbleformation. Secondly, addition of organic solvents in rigid PVC leads toa lowering of the Vicat value (80° C.), and to volatile organic vapoursin the course of extrusion and calendering (VOC problems).5. Particular organic perchlorate salts, specifically primary, secondaryand tertiary amine perchlorates are dangerous to handle owing to theirtendency to decompose spontaneously as NH perchlorates, and ammoniumperchlorate, as the last member in this series, is even used as a rocketfuel component. Moreover, amine perchlorates are not optimal in relationto their melting points. Quaternary ammonium perchlorates have not beendescribed before as thermal stabilizers for PVC, but have only a modestperformance as such stabilizers.6. The amines on which the amine perchlorates are based generally have ahighly degrading effect in PVC (e.g. nicotinic esters, formamide andtrioctylamine).

Quaternary ammonium perchlorates which have been proposed as PVCantistats and whose thermally stabilizing action in PVC is mentionedshould be treated with scepticism, since it has been found thatprecisely this compound class has thermally degrading action in PVC.

It is therefore an object of the present invention to providecompositions and stabilizer systems which alleviate the disadvantages ofthe prior art at least partly.

The object is achieved by a composition comprising at least onesynthetic polymer and at least one coordination-polymerictriethanolamineperchlorato(triflato)metal inner complex comprising themonomer unit of the formula (A):

where

Mt=Li, Na, K, Mg, Ca, Sr, Ba and Zn; An=OClO₃ or OS(O₂)CF₃;

q=1 or 2.

Furthermore, the object is achieved by a stabilizer system for syntheticpolymers, comprising a coordination-polymerictriethanolamineperchlorato(triflato)metal inner complex comprising themonomer unit of the formula (A):

where

Mt=Li, Na, K, Mg, Ca, Sr, Ba and Zn; An=OClO₃ or OS(O₂)CF₃;

q=1 or 2.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 a is a micrograph of a TEAP crystal at a first scale; and

FIG. 1 b is a micrograph of a TEAP crystal at a second scale.

It has been found that the inventive inner complexes (A) do not have atleast some of the disadvantages outlined in points 1-6. For instance,the novel compounds often exhibit a sharp m.p., and usually also melt ata lower temperature and without decomposition. The melting points arehigher than 80° C. but usually below 200° C., i.e. they have no adverseeffect on the Vicat (80° C.) value of the finished moulding and melthomogeneously at the processing temperatures, which prevents spotformation and solid particle inclusion. It is thus possible to producetransparent PVC articles. Homogeneous product distribution is ensured inthe course of hot mixing. The powder blends are not tacky owing to thelack of hygroscopicity, do not cake, do not agglomerate and arefree-flowing. The products can be stored under air without loss ofquality. The solids do not have any sharp-edged crystals, i.e. do nothave an abrasive effect in the course of processing. The incorporationinto a stable cage structure (metallatrane cage or aza cage)phlegmatizes the perchlorate group.

The thermally stabilizing action of these inner complexes, particularlyin the form of two-substance and three-substance combinations withinitial colour improvers (ICIs) and hydrogen chloride scavengers (SCVs)is enhanced significantly compared to that mentioned in the prior art(PA). These product properties were surprising. Perchlorato-TEA innercomplexes (TEA=triethanolamine) of lithium, sodium, strontium and bariumhave been described before in J. G. VERKADE et al., Inorg. Chem. 33,2137 (1994). For some of these inner complexes, an X-ray structuralanalysis (XSA) has already been carried out. For the sodium and bariuminner complexes, the following stoichiometry is found [(TEA)NaOClO₃]_(n)and [(TEA)₂Ba(OClO₃)₂]₂, the degree of oligomerization or polymerizationbeing evident from the XSA. The inner complexes are anhydrous. In thecase of the sodium inner complex¹⁾ with the m.p. of 129-130° C., the XSAshows the following image: the sodium cation has four ligands in thecoordination sphere; a TEA group acts as a tetradentate, non-bridgingκ-N O³ ligand, two bridging non-chelating TEA groups (μ-ligands) and aperchlorate anion with monodentate bonding. This gives rise to a totalcoordination number of seven for sodium. Since the perchlorate anionfunctions as a perchlorato ligand, these substances are included in theclass of the inner complexes. Surprisingly, such inner complexes aresuitable in stabilizer systems for synthetic polymers and incompositions comprising them. The synthetic polymer is preferably ahalogenated polymer, especially PVC. Owing to the particular suitabilityfor halogenated polymers, reference is made to them below in thedescription of the invention. However, it should be emphasized thatnon-halogenated synthetic polymers can also be stabilized in the contextof the present invention. The suitability of such a complex structure isalso surprising because the prior art (D. S. VAN ES in Catalytic HeatStabilizers: Fact or Fiction?—9^(th) Intern. PVC Conf., Brighton, April2005) states that perchlorate salts stabilize PVC effectively only whena “bare” perchlorate anion and hence a likewise “bare” metal cation arepresent. This can be equated with a non-coordinating perchlorate anionand a non-coordinating metal cation, which cannot be reconciled with thestructural features outlined for (A). All inventive compounds are solidsand comprise TEA as a tertiary alkanolamine as a complex ligand. 1)abbreviated to TEAP in this patent document.

It was also surprising that this specific ligand property of TEA, sincethe introduction of additional methyl groups (conversion from thetertiary alkanolamine TEA to the tertiary alkanolamine TIPA) changesthis complexation feature to such an extent that an attempt to prepareand isolate solid homologous TIPA complexes fails. It is likewiseimpossible to introduce a single methyl group or a long-chain(surfactant) radical into the TEA ligand, since the stable inner complex(cage) structure is disturbed here too.

The present invention further provides inner complexes of the formula(A), as specified above, where Mt=Li, Na or Ca; q=1 or 2 and An=OClO₃ orOS(O₂)CF₃; preferably, Mt=Li, Na; q=1 and An=OClO₃.

The present invention further provides inner complexes in which Mt═Caand q=2.

The following inner complexes are listed (where the followingabbreviations are used: perchlorato=Pc and triflato=Tf):

[(TEA) NaPc] [A-1], [(TEA) NaTf] [A-2], [(TEA) LiPc] [A-3], [(TEA) LiTf][A-4], [(TEA) KPc] [A-5], [(TEA) KTf] [A-6], [(TEA)₂ Mg(Pc)₂] [A-7],[(TEA)₂ Mg(Tf)₂] [A-8], [(TEA)₂ Ca(Pc)₂] [A-9], [(TEA)₂Ca(Tf)₂] [A-10],[(TEA)₂ Sr(Pc)₂] [A-11], [(TEA)₂ Sr(Tf)2] [A-12], [(TEA)₂Zn(Pc)₂][A-13], [(TEA)₂ (Zn/Tf)₂] [A-14], [(TEA)₂Ba(Pc)₂] [A-15],[(TEA)₂Ba(Tf)₂] [A-16].

The inventive inner complexes (A) are preferably used in the halogenatedpolymer at appropriately 0.001 to 5 phr, preferably 0.01 to 3 phr andvery particularly 0.01 to 2 phr.

The inner complexes (A) may be combined with further substance groups asfollows:

Linear or cyclic ureide and/or polyaminocrotonic esters and/orcyanamides of the formulae (B-1) and (B-2) and/or dihydropyridines ofthe formulae (C-1) and (C-2):

and

and

where

-   X=O or S; Y=CH₂CN, Z=H, or Y and Z form the bridging member    CH₂—C═NH, CR⁵═C—NHR⁶ or R¹R²C.-   R¹, R² are each independently H, C₁-C₂₂-alkyl, cyclohexyl,    (meth)allyl, oleyl, phenyl, benzyl, phenethyl, (tetrahydro)naphthyl,    meth (or eth)oxypropyl (or ethyl), CH₂—CHOH—R^(1a),    CH₂—CHOH—CH₂X′R^(1a);-   X′=O or S;-   R^(1a)=H, C₁₋₂₂-alkyl, cyclohexyl, (meth)allyl, oleyl, phenyl,    benzyl, phenethyl, (tetrahydro)naphthyl or meth (or eth)oxypropyl    (or ethyl);-   R³=unbranched or branched C₂-C₂₀-alkylene which may be interrupted    by 1 to 4 oxygen or sulphur atoms and/or may be substituted by 1 to    4 OH groups, or dimethylolcyclohexane-1,4-diyl, polyethylene (or    -propylene) glycol-α,ω-diyl (preferably, poly=tetra to deca),    polyglyceryl-α,ω-diyl (preferably, poly=tetra to deca) or    glyceroltriyl, trimethylolethane (or -propane)triyl,    pentaerythritoltri (or -tetra)yl, bis(trimethylolethane (or    -propane)tri (or -tetra))yl, diglyceroltri (or -tetra)yl,    tetritoltetrayl, triglyceroltri (or -tetra, -penta)yl,    pentitolpentayl, dipentaerythritolpenta (or -hexa)yl and    hexitolhexayl;-   n=2, 3, 4, 5 or 6;-   R⁵=H or (C₃-C₁₀-alkylidene)_(1/2); where this alkylidene may be    interrupted by up to 2 oxygen atoms or may have up to 2 substituents    selected independently from the group consisting of OH, phenyl and    hydroxyphenyl;-   R⁶=H, hydroxy-C₂-C₄-alkyl, 3-C₁-C₁₀-alkoxy-2-hydroxypropyl, or mono-    to trihydroxy-, mono- to tri-C₁-C₄-alkyl- or/and mono- to    tri-C₁-C₄-alkoxyphenyl, allyl, mono- to trisubstituted phenyl;-   R⁷, R^(7′) are each independently branched and unbranched    C₁-C₄-alkyl, phenyl, cyclohexyl;-   W=CO₂CH₃, CO₂C₂H₅, CO₂ ^(n)C₁₂H₂₅ or CO₂C₂H₄—S—^(n)C₁₂H₂₅;-   L, T=unsubstituted C₁₋₁₂-alkyl; and-   m and n′ are each integers of 0 to 20,-   k is 0 or 1 and-   R and R′ are each independently ethylene, propylene, butylene or an    alkylene- or cycloalkylenebismethylene group of the    —(C_(p)H_(2p)—X″—)_(t)C_(p)H_(2p)— type where p is an integer of 2    to 8, t is an integer of 0 to 10 and X″ is oxygen or sulphur.

The radicals specified in brackets are further alternative radicals; forinstance, polyethylene (or -propylene) glycol means polyethylene glycolor polypropylene glycol. This also applies hereinafter.

Likewise surprising was the finding that the combination of innercomplexes (A) with aminocrotonates or dihydropyridines (B-2, C-1, C-2)improves the transparency behaviour. For instance, transparencies ofmore than 90% can be achieved when formulation constituents whichotherwise impart transparency are used.

Preferred definitions of the substituents, empirical formulae andindices are as follows:

In the case of (B-1), in all cases, X═O or S. In linear ureides, Y═CH₂CNand Z=H. In the case of cyclic ureides, the bridging member Y-Z=CH₂—C═NHin the case of the 6(4)-imino-barbituric acids, the bridging memberY-Z=CR⁵═C—NHR⁶ in the case of the aminouracils, and the bridging memberY-Z=R¹R²C in the case of the hydantoins. In the case of (B-2), n=2, 3,4, 5 or 6.

The substituents R¹ and R² may be C₁-C₂₂-alkyl, specifically methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl and docosyl, wherethese radicals may be branched or unbranched. Preference is given toC₁-C₈-alkyl, particular preference being given to methyl, ethyl, propyland butyl. In addition, R¹ and R² may be cyclohexyl, (meth)allyl, oleyl,phenyl, benzyl, phenethyl, methoxyethyl, ethoxyethyl, methoxypropyl andethoxypropyl. Preference is given to allyl and phenethyl, cyclohexyl,benzyl, methoxypropyl and ethoxypropyl, particular preference tocyclohexyl, benzyl, methoxypropyl and ethoxypropyl.

Preferably, X═O and, more preferably, R¹═CH₃ and R²═CH₂—CHOH—R^(1a),where R^(1a) is preferably H, CH₃, C₂H₅, or R²═CH₂—CHOH—CH₂OR^(1a),where R^(1a) is preferably H or C₁-C₁₀-alkyl and allyl.

C₁-C₁₀-Alkyl includes, for example, methyl, ethyl, n-propyl, isopropyl,n-butyl, isobutyl, sec-butyl, tert-butyl, hexyl, heptyl, octyl,2-ethylhexyl, nonyl, decyl, neodecyl.

R⁵ is hydrogen or (C₃-C₁₀-alkylidene)_(1/2)—the index ½ states that theproducts are bis-products, i.e. alkylidenebis-6-aminouracils. Alkylidenegroups include ethylidene, propylidene, butylidene, pentylidene,hexylidene, heptylidene, octylidene, nonylidene and decylidene, and alsosalicylidene and cinnamylidene. The names apply to linear and branchedrepresentatives. Preference is given to propylidene, hexylidene,heptylidene and octylidene. Particular preference is given to hexylideneand heptylidene.

The substituent R⁶ denotes hydrogen and hydroxy-C₂-C₄-alkyl. The lattergroup includes 2-hydroxyethyl, 2- and 3-hydroxypropyl, and 2-, 3- and4-hydroxybutyl. Preference is given to 2-hydroxyethyl and to 2- and3-hydroxypropyl. Particular preference is given to hydrogen.

In addition, R⁶ is allyl or 3-C₁-C₁₀-alkoxy-2-hydroxypropyl. Thisincludes 3-methoxy-, 3-ethoxy-, 3-propoxy-, 3-butoxy-, 3-pentoxy-,3-hexoxy-, 3-heptoxy-, 3-octoxy-, 3-nonoxy- and3-decoxy-2-hydroxypropyl. Preference is given to allyloxy-, 3-butoxy-,3-octoxy- and 3-decoxy-2-hydroxypropyl.

In addition, the substituent R⁶ is mono- to trisubstituted phenyl, wherethe substituents may be hydroxyl or/and C₁-C₄-alkyl or/and C₁-C₄-alkoxy,and the combination of hydroxyl with methyl, ethyl, propyl and butyl,and of hydroxyl with methoxy, ethoxy, propoxy and butoxy. Preference isgiven to the hydroxyl, methyl, butyl, methoxy and ethoxy radical as thesubstituent. Particular preference is given to the hydroxyl and methoxygroup. Preference is given to mono- and disubstitution. However,particular preference is given to monosubstitution. Particularpreference is likewise given, in the case of polysubstitution, to thecombinations of hydroxyl with meth(eth)oxy or of hydroxyl withmonomethyl or dimethyl, and to the combinations of methyl, ethyl, propyland butyl with methoxy; ethoxy, propoxy and butoxy. Specific examplesinclude: 2-, 3- and 4-hydroxyphenyl; 2-hydroxy-4-methylphenyl;2-hydroxy-5-methylphenyl; 2-hydroxy-5-t-butylphenyl; and 2-, 3- and4-meth(eth)oxyphenyl.

The compounds (B-1) may also be present as hydrates. This is preferablythe case when Y and Z are CR⁵═C—NR⁶; more preferably when R¹ or/andR²≢methyl. The hydrates may be present, for example, in the form of thehemi-, sesqui- or dihydrate. High-melting cyclic ureides (m.p.: >180°C.) are preferably used in micronized form (particle size <50 μm).

For (B-2) containing R³ as C₂-C₂₀-alkylene which may be interrupted byfrom 1 to 4 oxygen or sulphur atoms or/and may be substituted by from 1to 4 OH groups, preference is given to ethanediyl-1,2, propanediyl-1,2,propanediyl-1,3, butanediyl-2,3, butanediyl-1,4, CH₂CH₂OCH₂CH₂,CH₂CH₂OCH₂CH₂OCH₂CH₂, CH₂CH₂SCH₂CH₂, CH₂CH₂OCH₂CH₂ OCH₂CH₂OCH₂CH₂,CH₂CH₂SCH₂CH₂SCH₂CH₂, C₃H₆OC₃H₆,C₃H₆OC₃H₆OC₃H₆C₃H₆OC₃H₆OC₃H₆OC₃H₆OC₃H₆CH₂CHOHCH₂OCH₂CHOHCH₂,CH₂CHOHCH₂OCH₂CHOHCH₂OCH₂CHOHCH₂. Particular preference is given toCH₂CH₂CH₂CH₂ and CH₂CH₂SCH₂CH₂. Tetritol is preferably erythritol,arabinitol and xylitol; hexitol is preferably mannitol and sorbitol.

Preferred representatives of the individual substance groups are listedbelow. The list is not restrictive but rather selective.

(B-1)—Linear acylureides (linear ureides, acylcarbamides, acylureas),such as [1] N,N′-dimethyl-, [2] N,N′-diethyl-, [3] N,N′-dipropyl-, [4]N,N′-diallyl-, [5] N,N′-dibutyl-, [6] N,N′-dioctyl-, [7] N,N′-didodecyl-and [8] N,N′-dibenzylcyanoacetureide, [9] N- or N′-monomethyl-, [10] N-or N′-monoethyl-, [11] N- or N′-monopropyl-, [12] N- or N′-monoallyl-,[13] N- or N′-monobutyl-, [14] N- or N′-monopentyl-, [15] N- orN′-monohexyl-, [16] N- or N′-monoheptyl- and [17] N- or N′-monooctyl-,[18] N,N′-monocyclohexyl-[19] N,N′-monobenzyl- and [20]N,N′-monophenylcyanoacetureide. Preference is given to [1], [2], [3],[4], [5], [8], [9], [10], [11], [12], [13], [18], [19] and [20].Particular preference is given to [1], [4], [8], [12], [18], [19] and[20]. Very particular preference is given to [1].

(B-1)—Cycloacylureides (cyclic ureides, 6(4)-iminobarbituric acids or6-iminohydrouracils or 6(4)-iminodihydropyrimidine-2,4-diones), such as[21] (CAS No. 17743-04-3) N,N′-dimethyl-, [22] N,N′-diethyl-, [23]N,N′-dipropyl-, [24] N,N′-diallyl-, [25] N,N′-dibutyl-, [26]N,N′-dioctyl- and [27] N,N′-didodecyl-, [28]N,N′-dibenzyl-6(4)-iminobarbituric acid, [29] (CAS No. 17743-03-2 and17743-02-1) N- or N′-monomethyl-, [30] N- or N′-monoethyl-, [31] N- orN′-monopropyl-, [32] N- or N′-monoallyl-, [33] N- or N′-monobutyl-, [34]N- or N′-monopentyl-, [35] N- or N′-monohexyl-, [36] N- orN′-monoheptyl-[37] N- or N′-monooctyl-, [38] N or N′-monocyclohexyl- or[39] N or N′-monophenyl- and [40] N,N′-monobenzyl-6-iminobarbituricacid. Preference is given to [21], [22], [23], [24], [25], [28], [29],[30], [31][32], [33], [37], [38], [39] and [40]. Particular preferenceis given to [21], [24], [28], [32], [37], [38], [39] and [40]. Veryparticular preference is given to [21].

(B-1)—Cycloacylureides (aminouracils or aminopyrimidine-2,4-diones),such as [41] N,N′-dimethyl-, [42] N,N′-diethyl-, [43] N,N′-dipropyl-,[44] N,N′-diallyl-, [45] N,N′-dibutyl-, [46] N,N′-dioctyl- and [47]N,N′-didodecyl-, [48] N,N′-dibenzyl-6-aminouracil, [49] N- orN′-monomethyl-, [50] N- or N′-monoethyl-, [51] N- or N′-monopropyl-,[52] N- or N′-monoallyl-, [53] N- or N′-monobutyl-, [54] N- orN′-monopentyl-, [55] N- or N′-monohexyl-, [56] N- or N′-monoheptyl-,[57] N- or N′-monooctyl-, [58] N- or N′-monocyclohexyl-, [59] N orN′-monobenzyl- and [60] N or N′-monophenyl-6-aminouracil. Preference isgiven to [41], [42], [43], [44], [45], [48], [49], [50], [51], [52],[53], [57], [58], [59] and [60]. Particular preference is given to [41],[44], [48], [52], [57], [58], [59] and [60]. Very particular preferenceis given to [41].

Preferred hydrates are the hemihydrate and monohydrate of [42], [43],[44] and [45].

This category also includes the 6-aminouracils substituted on theexocyclic nitrogen atom, such as hydroxyethylamino andhydroxypropylamino derivatives or hydroxyanilino-, methoxyanilino- andethoxyanilinouracils. Additionally mentioned are [61,62,63] N-2-, -3-and -4-hydroxyphenyl-1,3-dimethyl-6-aminouracil and [64]N-2-hydroxy-4-methylphenyl-, [65] N-2-hydroxy-5-methylphenyl-, [65]N-2-hydroxy-5-tert-butylphenyl-, [66,67,68] N-2-, -3- and-4-methoxyphenyl-, [69,70,71] N-2-, -3- and-4-ethoxyphenyl-1,3-dimethyl-6-aminouracil, [72] N-2-hydroxyethylamino-,[73] N-2-hydroxypropylamino-, [74] N-3-hydroxypropylamino-, [75]N-2-hydroxybutylamino-, [76] N-3-hydroxybutylamino- and [77]N-4-hydroxybutylamino-1,3-dimethyl-6-aminouracil. Preference is given to[61], [64], [65], [66], [69], [72], [73] and [74]. Particular preferenceis given to [61], [64], [65], [66] and [69]. Very particular preferenceis given to [61], [66] and [69]. The following should likewise bementioned here: 5-substituted 6-aminouracils, such asalkylidenebis-6-aminouracils. Also listed are [78] 5-ethylidene-, [79]5-propylidene-, [80] 5-(2-ethylbutylidene)-, [81] 5-hexylidene-, [82]5-heptylidene-, [83] 5-octylidene-, [84] 5-benzylidene-, [85]5-salicylidene-, [86] 5-(3-hydroxy)benzylidene-, [87]5-(4-hydroxy)benzylidene- and [88] 5-(2-hydroxy)-3-methoxybenzylidene-and [89] 5-pentylidenebis-1,3-dimethyl-6-aminouracil. Preference isgiven to [80], [81], [82], [83] and [89]. Particular preference is givento [81], [82], [83] and [89]. Very particular preference is given to[81] and [82].

Reaction of N-monosubstituted 6-aminouracils with C-glycidyl compoundsand glycidyl (thio)ethers or esters forms N,N′-disubstituted6-aminouracils. The following are mentioned by name: [90]1-methyl-3-(3-isopropoxy-2-hydroxypropyl)-, [91]1-phenyl-3-(3-isopropoxy-2-hydroxypropyl)-, [92]1-methyl-3-(3-tert-butoxy-2-hydroxypropyl)-, [93]1-benzyl-3-(3-isopropoxy-2-hydroxypropyl)-, [94]1-methyl-3-(3-neononylcarboxy-2-hydroxypropyl)-, [95]1-methyl-3-(2-hydroxypropyl)-, [96]1-methyl-3-(3-(2-ethylhexoxy-2-hydroxypropyl)-, [97]1-methyl-3-(2-hydroxyhexyl)-, [98] 1-benzyl-(2-hydroxypropyl)-, [99]1-methyl-(2-hydroxybutyl)-, [100] 1-benzyl-(2-hydroxybutyl)-, [101]1-benzyl-(3-isopropoxy-2-hydroxypropyl)-, [102]1-methyl-3-(2-hydroxyethyl)- and [103]1-methyl-3-(3-allyloxy-2-hydroxypropyl)-6-aminouracil. Preference isgiven to [90], [92], [94], [95], [96], [97], [99], [102] and [103].Particular preference is given to [90], [92], [95], [99], and [103].Very particular preference is given to [95], [99] and [103].

Certain aminouracils are available in the chemical trade: [1], [9] and[41] are “commodities” and are used as bulk chemicals in industrialcaffeine or theobromine synthesis. For 6(4)-iminobarbituric acids,relevant literature syntheses are available.

(B-1)—Hydantoins (imidazolidinediones), hydantoin [103a],2-thiohydantoin [103b], 5-methylhydantoin [103c], 5-phenylhydantoin[103d], 5-methyl-2-thiohydantoin [103e], 5-phenyl-2-thiohydantoin[103f], 5,5-dimethylhydantoin [103g], 5,5-dimethyl-2-thiohydantoin[103h], 5-methyl-5-phenylhydantoin [103i] and5-methyl-5-phenyl-2-thiohydantoin [103j]. Preference is given to [103a]and [103b]. Very particular preference is given to [103a].

(B-2) Bisaminocrotonic acid esters of [104] ethylene glycol and [105]propylene glycol and of polyethylene glycols and polypropylene glycolsand of [106] glycerol and polyglycerols. Trisaminocrotonic acid estersof [107] glycerol, [108,109] trimethylolethane(propane), [110]triethylol isocyanurate. Tetrakis(aminocrotonic esters) of [111]pentaerythritol, [112,113] bistrimethylolethane(propane),hexakis(aminocrotonic esters) of [114] dipentaerythritol and [115]sorbitol, and [116] butanediyl-1,4- and [117] thiobisethanediylaminocrotonate.

Preference is given to [104], [105], [108], [109], [111], [113], [116]and [117].

Particular preference is given to [104], [105], [116] and [117]. Veryparticular preference is given to [116] and [117]. Both compounds areproduced on an industrial scale.

(C-1) Monomeric dihydropyridines, such as methyldimethyldihydropyridinedicarboxylate [118], ethyldimethyldihydropyridinedicarboxylate [119] and dilauryldimethyldihydropyridinedicarboxylate [120] (a compound which is producedon the industrial scale).

(C-2) Oligo- and polydihydropyridines which derive from 1,4-butanediolbis-3-aminocrotonate or thiodiglycol bis-3-aminocrotonate and the endmembers methyl or ethyl 3-aminocrotonate, specifically thebis(dihydropyridines) [121] and [122] (sulphur-free), and also [123] and[124] (sulphur-containing). And also the polydihydropyridines [125] and[126] (sulphur-free), and also [127] and [128] (sulphur-containing).[127] and [128] are commercial products.

Preferred two-substance or multisubstance combinations of at least oneinitial colour improver (ICI)+at least one booster (A) are:

(B-1): R¹ or R²=methyl, ethyl, propyl, butyl, cyclohexyl, allyl, benzylor hydrogen and (A).

(B-2): Bisaminocrotonic esters of 1,4-butanediol or/and of thiodiglycoland (A).

Specified preferred two-substance or multisubstance combinations are:

1. Two-substance or multisubstance combinations of at least one compound(B-1) with at least one booster (A), specifically:

(B-1) component—linear acylureides:

[1] with [A-1], [A-2], [A-3], [A-4] and [A-5],

very particular preference being given to the combination with [A-1].

(B-1) component—cyclic acylureides (6(4)-iminobarbituric acids):

[21] with [A-1], [A-2], [A-3], [A-4] and [A-5],

very particular preference being given to the combination with [A-1].

(B-1) component—cyclic acylureides (aminouracils):

[41] with [A-1], [A-2], [A-3], [A-4] and [A-5],

[61] with [A-1], [A-2], [A-3], [A-4] and [A-5],

[66] with [A-1], [A-2], [A-3], [A-4] and [A-5],

[69] with [A-1], [A-2], [A-3], [A-4] and [A-5],

[81] with [A-1], [A-2], [A-3], [A-4] and [A-5],

[82] with [A-1], [A-2], [A-3], [A-4] and [A-5],

[95] with [A-1], [A-2], [A-3], [A-4] and [A-5],

[99] with [A-1], [A-2], [A-3], [A-4] and [A-5],

[103] with [A-1], [A-2], [A-3], [A-4] and [A-5],

very particular preference being given to the combination of [41] with[A-1].

(B-1) component—cyclic acylureides (hydantoins)

[103a] with [A-1], [A-2], [A-3], [A-4] and [A-5],

[103b] with [A-1], [A-2], [A-3], [A-4] and [A-5],

very particular preference being given to the combination of [103a] with[A-1].

2. Two-substance or multisubstance combinations of at least one compound(B-2) with at least one booster (A), specifically:

[116] with [A-1], [A-2], [A-3], [A-4] and [A-5],

[117] with [A-1], [A-2], [A-3], [A-4] and [A-5],

very particular preference being given to the combinations with [A-1].

3. Two-substance or multisubstance combinations of at least one compound(C-1) with at least one booster (A), specifically:

[118] with [A-1], [A-2], [A-3], [A-4] and [A-5],

[120] with [A-1], [A-2], [A-3], [A-4] and [A-5],

very particular preference being given to the combination of [120] with[A-1].

4. Two-substance or multisubstance combinations of at least one compound(C-2) with at least one booster (A), specifically:

[127] with [A-1], [A-2], [A-3], [A-4] and [A-5],

[128] with [A-1], [A-2], [A-3], [A-4] and [A-5],

very particular preference being given to the combinations with [A-1].

It will be appreciated that the compounds of classes (B-1), (B-2), (C-1)and (C-2) may also, just like the boosters [A-1], [A-2], [A-3], [A-4]and [A-5], be combined with one another.

The compounds from groups (A) and (B) are used in the halogenatedpolymer appropriately at 0.01 to 10 phr, preferably 0.05 to 5 phr andespecially 0.1 to 3 phr, preference being given to values in the lowerthreshold region for (A).

In addition, it is possible to use combinations with various HClscavengers, such as:

Alkali Metal and Alkaline Earth Metal Compounds

This is understood to mean principally the carboxylates of the acidsdescribed in the “zinc compounds” chapter, but also corresponding oxidesor hydroxides or carbonates. Also useful are mixtures thereof withorganic acids. Examples are LiOH, NaOH, KOH, CaO, Ca(OH₂), MgO, Mg(OH)₂,Sr(OH)₂, Al(OH)₃, CaCO₃ and MgCO₃ (including basic carbonates, forexample magnesia, alba and huntite), and also fatty acid salts of sodiumand potassium. In the case of alkaline earth metal and zinccarboxylates, it is also possible to use their adducts with MO or M(OH)₂(M=Ca, Mg, Sr or Zn), so-called “overbased” compounds. Preference isgiven to using alkali metal, alkaline earth metal and/or aluminiumcarboxylates in addition to the inventive stabilizers.

Preference is given to magnesium hydroxide, magnesium acetylacetonate,calcium acetylacetonate, and uncoated and coated calcium hydroxide. Veryparticular preference is given to coated calcium hydroxide (coating withfatty acids, for example palmitic and stearic acids, or mixturesthereof).

Metal Soaps

Metal soaps are mainly metal carboxylates, preferably relativelylong-chain carboxylic acids. Familiar examples are stearates andlaurates, and also oleates and salts of relatively short-chain aliphaticor aromatic carboxylic acids, such as acetic acid, propionic acid,butyric acid, valeric acid, hexanoic acid, sorbic acid; oxalic acid,malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid,citric acid, benzoic acid, salicylic acid, phthalic acids, hemimelliticacid, trimellitic acid, pyromellitic acid.

The metals include: Li, Na, K, Mg, Ca, Sr, Ba, Zn, Al, La, Ce and rareearth metals. Often, so-called synergistic mixtures such as barium/zinc,magnesium/zinc, calcium/zinc or calcium/magnesium/zinc stabilizers areused. The metal soaps may be used individually or in mixtures. Anoverview of common metal soaps can be found in Ullmanns Encyclopedia ofIndustrial Chemistry, 5th Ed., Vol. A16 (1985), p. 361 ff. Preference isgiven to magnesium, potassium and zinc soaps.

Preference is given to magnesium and calcium soaps. Very particularpreference is given to magnesium laurate, magnesium stearate, calciumlaurate and calcium stearate.

Zinc Compounds:

The organic zinc compounds with a Zn—O bond are zinc enolates, zincphenoxides or/and zinc carboxylates. The latter are compounds from thegroup of the aliphatic saturated and unsaturated C₁₋₂₂-carboxylates, ofthe aliphatic saturated or unsaturated C₂₋₂₂-carboxylates which aresubstituted by at least one OH group or whose chain is interrupted byone or more oxygen atoms (oxa acids), of the cyclic and bicycliccarboxylates having 5-22 carbon atoms, of the unsubstituted, at leastmono-OH-substituted and/or C₁-C₁₆-alkyl-substituted phenyl carboxylates,of the phenyl-C₁-C₁₆-alkyl carboxylates, or of the optionallyC₁₋₁₂-alkyl-substituted phenoxides, or of abietic acid. Zn—S compoundsare, for example, zinc mercaptides, zinc mercaptocarboxylates and zincmercaptocarboxylic esters.

As examples, mention should be made by name of zinc salts of monovalentcarboxylic acids, such as formic acid, acetic acid, propionic acid,butyric acid, valeric acid, hexanoic acid, enanthic acid, octanoic acid,neodecanoic acid, 2-ethylhexanoic acid, pelargonic acid, decanoic acid,undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid,palmitic acid, lauric acid, isostearic acid, stearic acid,12-hydroxystearic acid, 9,10-dihydroxystearic acid, oleic acid,ricinoleic acid, 3,6-dioxaheptanoic acid, 3,6,9-trioxadecanoic acid,behenic acid, benzoic acid, p-tert-butylbenzoic acid,dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid,toluic acid, dimethylbenzoic acid, ethylbenzoic acid, n-propylbenzoicacid, salicylic acid, p-tert-octylsalicylic acid, and sorbic acid,cinnamic acid, mandelic acid, glycolic acid; zinc salts of the divalentcarboxylic acids and monoesters thereof, such as oxalic acid, malonicacid, succinic acid, glutaric acid, adipic acid, fumaric acid,pentane-1,5-dicarboxylic acid, hexane-1,6-dicarboxylic acid,heptane-1,7-dicarboxylic acid, octane-1,8-dicarboxylic acid,3,6,9-trioxadecane-1,10-dicarboxylic acid, lactic acid, malonic acid,maleic acid, tartaric acid, malic acid, salicylic acid,polyglycoldicarboxylic acid (n=10-12), phthalic acid, isophthalic acid,terephthalic acid and hydroxyphthalic acid; and the di- or triesters ofthe tri- or tetravalent carboxylic acids, such as hemimellitic acid,trimellitic acid, pyromellitic acid, citric acid, and also so-calledoverbased zinc carboxylates or zinc laurylmercaptide, zincthioglycolate, zinc thiosalicylate, zinc bis-i-octylthioglycolate, zincmercaptopropionate, zinc thiolactate, zinc thiomalate, zincbis(octylmercaptopropionate), zinc bis(isooctylthiolactate) and zincbis(laurylthiomalate).

The zinc enolates are preferably enolates of acetylacetacetone, ofbenzoylacetacetone, of dibenzoylmethane, and also enolates ofacetoacetoacetic and benzoylacetic esters, and of dehydroacetic acid. Inaddition, it is also possible to use inorganic zinc compounds such aszinc oxide, zinc hydroxide, zinc carbonate, basic zinc carbonate or zincsulphide.

Preference is given to neutral or basic zinc carboxylates of acarboxylic acid having from 1 to 22 carbon atoms (zinc soaps), forexample benzoates or alkanoates, preferably C₈-alkanoates, stearate,oleate, laurate, palmitate, behenate, versatate, hydroxystearates and-oleates, dihydroxystearates, p-tert-butylbenzoate or (iso)octanoate.Particular preference is given to stearate, oleate, versatate, benzoate,p-tert-butylbenzoate and 2-ethylhexanoate.

The metal soaps or mixtures thereof may be employed in an amount of, forexample, from 0.001 to 10 parts by weight, appropriately from 0.01 to 8parts by weight, more preferably from 0.05 to 5 parts by weight, basedon 100 parts by weight of PVC.

Hydrotalcites

The chemical composition of these compounds is known to those skilled inthe art, for example from the publications PS-DE 38,43,581 A1, U.S. Pat.No. 4,000,100, EP 0,062,813 A1 and WO 93/20135. These may be based onAl/Mg/carbonate, Al/Mg/Ti/carbonate, Li/Mg/carbonate orLi/Al/Mg/carbonate, as described in PS-DE 102,17,364 A1 (SüdChemie),PS-DE 44,25266 A1 (Metallgesellschaft), PS-EP 0,549,340 A1 (MizusawaInd. Chem) and PS-JP 0,761,756 A1 (Fuji Chem. Ind.). Compounds from thegroup of the hydrotalcites can be described by the following generalformula:

M²⁺ _(1−x)M³⁺ _(x)(OH)₂(A^(n))_(x/b) *dH₂O

whereM²⁺=a cation of one or more of the metals from the group of Mg, Ca, Sr,Zn and Sn, M³⁺=an A1 or B cation, A^(n) is an anion with the valency −n,b=n, a number of 1-2, 0≦x≦0.5, d is a number of 0-20. Preference isgiven to compounds whereA^(n)═OH⁻, ClO₄ ⁻, HCO₃ ⁻, CH₃COO⁻, C₆H₅COO⁻, CO₃ ²⁻, (CHOHCOO)₂ ²⁻,(CH₂COO)₂ ²⁻, CH₃CHOHCOO⁻, HPO₃ ⁻ or HPO₄ ²⁻.

Examples of hydrotalcites are

Al₂O₃*6MgO*CO*12H₂O, Mg_(4.5)Al₂(OH)₁₃*CO₃*3.5H₂O, 4MgO*Al₂O₃*CO₂.9H₂O,4MgO*Al₂O₃*CO₂6*H₂O, ZnO*3MgO*Al₂O₃*CO₂*8-9H₂O andZnO*3MgO*Al₂O₃*CO₂*5-6H₂O

Particular preference is given to the Alkamizer 1 and 2 types, AlkamizerP 93-2 (manufacturer: Kyowa Chemical Ind. Co., Japan) and L-CAM(lithium-modified hydrotalcite=Lithium/Carbonate/Aluminium/Magnesium,manufacturer: Fuji Chem. Ind. Co. Ltd., Japan: PS-EP 0761 756 A1, orMizusawa Industrial Chemicals, Ltd.: PS-EP 0549 340 A1, andMetallgesellschaft AG: PS-DE 4425266 C1). Very particular preference isgiven to using dewatered hydrotalcites.

Titanium-Containing Hydrotalcites

Titanium-containing hydrotalcites are described in PS-WO 95/21127.Compounds of this type with the general formulaAl_(a)Mg_(b)Ti_(c)(OH)_(d)(CO₃)_(e)*mH₂O, where a:b=1:1 to 1:10; 2≦b≦10;

0<c<5; 0≦m<5, and d and e are selected so as to form a basic,charge-free molecule, may likewise also be used.

Lithium Sheet Lattice Compounds (Lithium Hydrotalcites)

Lithium aluminium sheet lattice compounds have the general formula:

Li_(a)M^(II) _((b−2a))Al_((2+a))OH_((4+2b))(A^(n−))_((2/n)) *mH₂O

in which

M^(II) is Mg, Ca or Zn and

A^(n) is a selected anion of the valency n or a mixture of anions andthe indices are in the range of0<a<(b−2)/2,1<b<6 andm=0 to 30,with the restriction that (b−2a)>2, orthe general formula:

[Al₂(Li_((1−x)).M^(II) _(x))(OH)₆]_(n)(A^(n−))_((1+x)) *mH₂O

in whichM^(II), A, m and n are each as defined above andx satisfies the condition that 0.01≦x<1.

In the preparation of the sheet lattice compounds mentioned, lithiumhydroxide, lithium oxide and/or compounds thereof which can be convertedto hydroxide, metal(II) hydroxides, oxides and/or compounds of themetals mentioned which can be converted to hydroxides, and aluminiumhydroxides and/or compounds thereof which can be converted tohydroxides, and also acids and/or salts thereof or mixtures thereof, arereacted with one another in the aqueous medium at a pH of 8 to 10 and attemperatures of 20 to 250° C., and the resulting solid reaction productis removed.

The reaction time is preferably 0.5 to 40 hours, especially 3 to 15hours. The reaction product obtained directly from the reactiondescribed above can be removed from the aqueous reaction medium by knownprocesses, preferably by filtration. The reaction product removed islikewise worked up in a manner known per se, for example by washing thefiltercake with water and drying the washed residue at temperatures of,for example, 60 to 150° C., preferably at 90 to 120° C.

For the reaction with aluminium, it is possible to use either finelydivided active metal(III) hydroxide in combination with sodiumhydroxide, or NaAlO₂. Lithium or one of the metal(II) compoundsmentioned can be used in the form of finely divided lithium oxide orhydroxide or mixtures thereof, or of finely divided metal(II) oxide orhydroxide or mixtures thereof. The corresponding acid anions can be usedin differently concentrated form, for example, directly as an acid orelse as a salt.

The reaction temperatures are preferably between about 20 and 250° C.,more especially between about 60 and 180° C. Catalysts or accelerantsare not required. In the substances, the water of crystallization can beremoved completely or partly by treatment. When they are used asstabilizers, the dried sheet lattice compounds do not release any wateror another gas at the processing temperatures of 160 to 220° C.customary for PVC, such that no troublesome bubble formation occurs inthe mouldings.

The anions A^(n) in the above general formula may be sulphate, sulphite,sulphide, thiosulphate, peroxosulphate, peroxodisulphate,hydrogenphosphate, hydrogenphosphite, carbonate, halides, nitrate,nitrite, hydrogensulphate, hydrogencarbonate, hydrogensulphite,hydrogensulphide, dihydrogenphosphate, dihydrogenphosphite,monocarboxylic acid anions such as acetate and benzoate, amide, azide,hydroxide, hydroxylamine, hydroazide, acetylacetonate, phenoxide,pseudohalides, halogenites, halogenates, perhalogenates, I₃ ⁻,permanganate, dianions of dicarboxylic acids such as phthalate, oxalate,maleate or fumarate, bisphenoxides, phosphate, pyrophosphate, phosphite,pyrophosphite, trianions of tricarboxylic acids such as citrate,trisphenoxides and many others, and also mixtures thereof. Among these,preference is given to hydroxide, carbonate, phosphite and maleate. Toimprove the dispersibility of the substances in halogenatedthermoplastic polymer materials, they may be surface-treated with ahigher fatty acid, for example stearic acid, an anionic surface-activeagent, a silane coupler, a titanate coupler or a glyceryl fatty acidester.

Calcium Aluminium Hydroxo Hydrogenphosphites

Compounds from the group of basic calcium aluminium hydroxyhydrogenphosphites of the general formula

Ca_(x)Al₂(OH)_(2(x+2))HPO₃.H₂O

where x=2-8 and

Ca_(x)Al₂(OH)_(2(x+3−y))(HPO₃)_(y) .mH₂O

where x=2-12,

$\frac{{2\; x} + 5}{2} > y > 0$

and m=0-12, excluding y=1 when x=2-8,suitable for the inventive stabilizer combinations can be prepared, forexample, by means of a process in which mixtures of calcium hydroxideand/or calcium oxide, aluminium hydroxide and sodium oxide, or ofcalcium hydroxide and/or calcium oxide and sodium aluminate are reactedwith phosphorous acid in amounts corresponding to the preparation of thedesired calcium aluminium hydroxy hydrogenphosphites in an aqueousmedium, and the reaction product is removed and recovered in a mannerknown per se. The reaction product obtained directly from the reactiondescribed above can be removed from the aqueous reaction medium by knownprocesses, preferably, for example, by washing the filtercake with waterand drying the washed residue at temperatures of, for example, 60-130°C., preferably 90-120° C.

For the reaction, it is possible to use either finely divided activealuminium hydroxide in combination with sodium hydroxide, or a sodiumaluminate. Calcium may be used in the form of finely divided calciumoxide or calcium hydroxide or mixtures thereof. The phosphorous acid maybe used in different concentrated form. The reaction temperatures arepreferably between 50 and 100° C., more preferably between about 60 and85° C. Catalysts or accelerants are not required, but are notdisruptive. In the compounds, the water of crystallization can beremoved completely or partly by thermal treatment.

When they are employed as stabilizers, the dried calcium aluminiumhydroxy phosphites do not release any water at the processingtemperatures of 160-200° C. which are customary, for example, for rigidPVC, so that no troublesome bubble formation occurs in the mouldings.

To improve their dispersibility in halogenated thermoplastic resins, thecompounds can be coated with surfactants in a known manner. The compoundclass, also referred to as CHAP or CAP compounds, is described in EP0,506,831 A1.

The above-described calcium aluminium hydroxo hydrogenphosphites andtitanium-containing hydrotalcites may be present, apart from incrystalline form, also in partly crystalline and/or amorphous form.

Zeolites (Alkali Metal or Alkaline Earth Metal Aluminosilicates)

They may be described by the formula M_(x/n)[(AlO₂)_(x)(SiO₂)_(y)]*wH₂Oin which n is the charge of the cation M; M is an element of the firstor second main group, such as Li, Na, K or NH₄, and Mg, Ca, Sr or Ba;y:x is a number of 0.8 to 15, preferably of 0.8 to 1.2; and w is anumber of 0 to 300, preferably of 0.5 to 30.

Examples of zeolites are sodium aluminosilicates of the formulaeNa₁₂Al₁₂Si₁₂O₄₈*27H₂O [zeolite A], Na₆Al₆Si₆O₂₄*2NaX*7.5H₂O, X═OH,halogen, ClO₄ [sodalite]; Na₆Al₆Si₃₀O₇₂*24H₂O; ClO₄ [Sodalith];Na₆Al₆Si₃₀O₇₂*24H₂O; Na₈Al₈Si₄₀O₉₆*24H₂O; Na₁₆Al₁₆Si₂₄O₈₀*16H₂O;Na₁₆Al₁₆Si₃₂O₉₆*16H₂O; Na₅₆Al₅₆Si₁₃₆O₃₈₄*250H₂O Na₅₆Al₅₆Si₁₃₆O₃₈₄*250H₂O[zeolite Y], Na₈₆Al₈₆Si₁₀₆O₃₈₄*264H₂O [zeolite X]; Na₂O, Al₂O₃,(2-5)SiO₂, (3.5-10)H₂O [zeolite P]; Na₂O, Al₂O₃, 2SiO₂*(3.5-10)H₂O(zeolite MAP); or the zeolites preparable by partial or completeexchange of the sodium atoms for lithium, potassium, magnesium, calcium,strontium or zinc atoms, such as (Na,K)₁₀Al₁₀Si₂₂O₆₄*20H₂O;Ca_(4.5)Na₃[(AlO₂)₁₂(SiO₂)₁₂]*30H₂O; K₉Na₃[(AlO₂)₁₂(SiO₂)₁₂]*27H₂O. Veryparticular preference is given to Na zeolite A and Na zeolite MAP (seealso PS-U.S. Pat. No. 6,531,533). Equally preferred are zeolites with anexceptionally small particle size, especially of the Na-A and Na—P type,as also described in PS-U.S. Pat. No. 6,096,820.

Dawsonites (Alkali Metal Aluminocarbonates)

These are described by the general formula

M[Al(OH)₂CO₃](M=Na,K).

The preparation of Na dawsonite (DASC or SAC) and K dawsonites (DAPC) ispublished in PS-U.S. Pat. No. 3,501,264 and U.S. Pat. No. 4,221,771, andalso in PS-EP 0394,670 A1. The synthesis can be effected hydrothermallyor non-hydrothermally. The products may be present in crystalline oramorphous form. Also included in the substance class are sodiummagnesium aluminocarbonates (SMACs); their preparation is described inPS-US 455,055,284.

The hydrotalcites and/or calcium aluminium hydroxo hydrogenphosphitesand/or zeolites and/or dawsonites may be employed in amounts of, forexample, 0.1 to 20 parts by weight, appropriately 0.1 to 10 parts byweight and especially 0.1 to 5 parts by weight, based on 100 parts byweight of halogenated polymer.

Glycidyl Compounds

They contain the glycidyl group

which is bonded directly to carbon, oxygen, nitrogen or sulphur atoms,and in which either R₃ and R₅ are both hydrogen, R₄ is hydrogen ormethyl and n=0, or in which R₃ and R₅ together are —CH₂—CH₂— or—CH₂—CH₂—CH₂—, R₄ is then hydrogen and n=0 or 1.

I) Glycidyl and β-methylglycidyl esters obtainable by reacting acompound having at least one carboxyl group in the molecule andepichlorohydrin or glyceryl dichlorohydrin or β-methylepichlorohydrin.The reaction is effected appropriately in the presence of bases.

The compounds having at least one carboxyl group in the moleculeemployed may be aliphatic carboxylic acids. Examples of these carboxylicacids are glutaric acid, adipic acid, pimelic acid, suberic acid,azelaic acid, sebacic acid, or dimerized or trimerized linoleic acid,acrylic and methacrylic acid, caproic acid, caprylic acid, lauric acid,myristic acid, palmitic acid, stearic acid and pelargonic acid, and alsothe acids mentioned for the organic zinc compounds.

However, it is also possible to use cycloaliphatic carboxylic acids, forexample cyclohexanecarboxylic acid, tetrahydrophthalic acid,4-methyltetrahydrophthalic acid, hexahydrophthalic acid or4-methylhexahydrophthalic acid.

In addition, it is possible to use aromatic carboxylic acids, forexample benzoic acid, phthalic acid, isophthalic acid, trimellitic acidor pyromellitic acid.

It is likewise also possible to use carboxyl-terminated adducts, forexample of trimellitic acid and polyols, for example glycerol or2,2-bis(4-hydroxycyclohexyl)propane.

Further epoxide compounds usable in the context of this invention can befound in EP 0 506 617.

II) Glycidyl or β-methylglycidyl ethers obtainable by reacting acompound having at least one free alcoholic hydroxyl group and/orphenolic hydroxyl group with a suitably substituted epichlorohydrinunder alkaline conditions, or in the presence of an acidic catalyst andsubsequent alkali treatment.

Ethers of this type derive, for example, from acyclic alcohols, such asethylene glycol, diethylene glycol and higher poly(oxyethylene)glycols,propane-1,2-diol, or poly(oxypropylene)glycols, propane-1,3-diol,butane-1,4-diol, poly(oxytetramethylene)glycols, pentane-1,5-diol,hexane-1,6-diol, hexane-2,4,6-triol, glycerol, 1,1,1-trimethylolpropane,bistrimethylolpropane, pentaerythritol, sorbitol, and also frompolyepichlorohydrins, butanol, amyl alcohol, pentanol, and also frommonofunctional alcohols such as isooctanol, 2-ethylhexanol, isodecanol,and also C₇-C₉-alkanol and C₉-C₁₁-alkanol mixtures.

However, they also derive, for example, from cycloaliphatic alcoholssuch as 1,3- or 1,4-dihydroxycyclohexane,bis(4-hydroxycyclohexyl)methane, 2,2-bis(4-hydroxycyclohexyl)-propane or1,1-bis(hydroxymethyl)cyclohex-3-ene, or they have aromatic rings suchas N,N-bis(2-hydroxyethyl)aniline orp,p′-bis(2-hydroxyethylamino)diphenylmethane.

The epoxide compounds may also derive from monocyclic phenols, forexample from phenol, resorcinol or hydroquinone; or they are based onpolycyclic phenols, for example bis(4-hydroxyphenyl)methane,2,2-bis(4-hydroxyphenyl)propane,2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 4,4′-dihydroxydiphenylsulphone, or condensation products, obtained under acidic conditions, ofphenols with formaldehyde, such as phenol novolacs.

Further possible terminal epoxides are, for example: glycidyl 1-naphthylether, glycidyl 2-phenylphenyl ether, 2-biphenyl glycidyl ether,N-(2,3-epoxypropyl)phthalimide and 2,3-epoxypropyl 4-methoxyphenylether.

III) N-Glycidyl compounds obtainable by dehydrochlorinating the reactionproducts of epichlorohydrin with amines which contain at least one aminohydrogen atom. These amines are, for example, aniline, N-methylaniline,toluidine, n-butylamine, bis(4-aminophenyl)methane, m-xylylenediamine orbis(4-methylaminophenyl)methane, but alsoN,N,O-triglycidyl-m-aminophenol or N,N,O-triglycidyl-p-aminophenol.

However, the N-glycidyl compounds also include N,N′-di-, N,N′,N″-tri-and N,N′,N″,N′″-tetraglycidyl derivatives of cycloalkyleneureas, such asethyleneurea or 1,3-propyleneurea, and N,N′-diglycidyl derivatives ofhydantoins, such as of 5,5-dimethylhydantoin or glycoluril andtriglycidyl isocyanurate.

IV) S-Glycidyl compounds, for example di-S-glycidyl derivatives whichderive from dithiols, for example ethane-1,2-dithiol orbis(4-mercaptomethylphenyl)ether.

V) Epoxide compounds having a radical of the above formula, in which R₁and R₃ together are —CH₂—CH₂— and n is 0, arebis(2,3-epoxycyclopentyl)ether, 2,3-epoxycyclopentylglycidyl ether or1,2-bis(2,3-epoxycyclopentyloxy)ethane. An epoxy resin with a radical ofthe above formula in which R₁ and R₃ together are —CH₂—CH₂— and n is 1is, for example, (3′,4′-epoxy-6′-methylcyclohexyl)methyl3,4-epoxy-6-methylcyclohexanecarboxylate.

Suitable terminal epoxides are, for example:

a) liquid bisphenol A diglycidyl ethers such as Araldit®GY 240,Araldit®GY 250, Araldit®GY 260, Araldit®GY 266, Araldit®GY 2600,Araldit®MY 790 and Epicote® 828 (BADGE);b) solid bisphenol A diglycidyl ethers such as Araldit®GT 6071,Araldit®GT 7071, Araldit®GT 7072, Araldit®GT 6063, Araldit®GT 7203,Araldit®GT 6064, Araldit®GT 7304, Araldit®GT 7004, Araldit®GT 6084,Araldit®GT 1999, Araldit®GT 7077, Araldit®GT 6097, Araldit®GT 7097,Araldit®GT 7008, Araldit®GT 6099, Araldit®GT 6608, Araldit®GT 6609,Araldit®GT 6610 and Epikote® 1002;c) liquid bisphenol F diglycidyl ethers such as Araldit®GY 281,Araldit®PY 302, Araldit®PY 306 (BFDGE);d) solid polyglycidyl ethers of tetraphenylethane, such as CG EpoxyResin®0163;e) solid and liquid polyglycidyl ethers of phenol-formaldehyde novolac,such as EPN 1138, EPN 1139, GY 1180, PY 307 (NODGE);f) solid and liquid polyglycidyl ethers of o-cresol-formaldehydenovolac, such as ECN 1235, ECN 1273, ECN 1280, ECN 1299 (NODGE);g) liquid glycidyl ethers of alcohols, such as Shell Glycidylether® 162,Araldit®DY 0390, Araldit®DY 0391;h) liquid and solid glycidyl esters of carboxylic acids, such as ShellCardura® E terephthalic esters, trimellitic esters and mixtures thereof,Araldit®PY 284 and Araldit®P811;i) solid heterocyclic epoxy resins (triglycidyl isocyanurate) such asAraldit®PT 810;j) liquid cycloaliphatic epoxy resins such as Araldit®CY 179;k) liquid N,N,O-triglycidyl ethers of p-aminophenol, such as Araldit®MY0510;l) tetraglycidyl-4,4′-methylenebenzamine orN,N,N′,N′-tetraglycidyldiaminophenyl-methane such as Araldit® MY 720,Araldit® MY 721.

Preference is given to using epoxide compounds having two functionalgroups. However, it is also possible in principle to use epoxidecompounds having one, three or more functional groups.

Predominantly epoxide compounds, in particular diglycidyl compounds,having aromatic groups are used.

If appropriate, it is also possible to use a mixture of differentepoxide compounds.

Particularly preferred terminal epoxide compounds are diglycidyl ethersbased on bisphenols, for example on 2,2-bis(4-hydroxyphenyl)propane(bisphenol A), bis(4-hydroxyphenyl)methane or mixtures ofbis(ortho/para-hydroxyphenyl)methane (bisphenol F).

The terminal epoxide compounds can be used in an amount of preferably atleast 0.1 part, for example 0.1 to 50 parts, appropriately 1 to 30 partsand especially 1 to 25 parts by weight, based on 100 parts by weight ofPVC.

Very particular preference is given to bisglycidyl alcohol ethers of theformula (D)

-   -   where    -   R³=unbranched or branched C₂-C₂₀-alkylene which may be        interrupted by 1 to 4 oxygen or sulphur atoms and/or may be        substituted by 1 to 4 OH groups, or        dimethylolcyclohexane-1,4-diyl, polyethylene (or        -propylene)glycol-α,ω-diyl (preferably poly is tetra to deca),        polyglyceryl-α,ω-diyl (preferably poly is tetra to deca) or        glyceroltriyl, trimethylolethane (or -propane)triyl,        pentaerythritoltri (or -tetra)yl, bistrimethylolethane (or        -propane)tri (or -tetra)yl, diglyceroltri (or -tetra)yl,        tetritoltetrayl, triglyceroltri (or -tetra, -penta)yl,        pentitolpentayl, dipentaerythritolpenta (or -hexa)yl and        hexitolhexayl;    -   and m=2, 3, 4, 5 or 6.

Also suitable are bisglycidyl alcohol ethers of alkanediols, diglycols,tri- and tetraglycols (glycol=ethylene glycol or propylene glycol) andpolyglycols, and also of [118a] glycerol and polyglycerols, and also of1,4-cyclohexanedimethanol [118b]. Tris(epoxypropyl alcohol ethers) of[119a] glycerol and [120a, 121a] trimethylolethane(-propane) and also of[121b, 121c] triethylol(-isopropylol) isocyanurate (THEIC) andtetrakis(epoxypropyl alcohol ethers) of [122a, 123a]bis(trimethylolethane(-propane)) and hexakis(epoxypropyl alcohol ethers)of [124a] dipentaerythritol and [125a] sorbitol. Particular mentionshould be made of [126a] hexanediol diglycidyl ether and [127a]neopentyl glycol diglycidyl ether, and also [128a]ethylene glycoldiglycidyl ether, [129] diethylene glycol diglycidyl ether and [130]dipropylene glycol diglycidyl ether, and also polyglycerol diglycidylether, [131] diglycerol diglycidyl ether, [132] triglycerol diglycidylether, [133] tetraglycerol diglycidyl ether and [134] pentaglyceroldiglycidyl ether, [135] 1,4-butanediol diglycidyl ether, [136, 137]trimethylolethane(propane) diglycidyl ether, and [138, 139]pentaerythritol tri- and tetraglycidyl ether and polyglyceroltriglycidyl ether. Preference is given to [118a], [118b], [119a],[120a], [121a], [126a], [127a], [128a], [129], [130], [131], [132],[133], [134], [135], [136], [137], [138] and [139]. Particularpreference is given to [118a], [188b], [119a], [120a], [121a], [126a],[127a], [128a], [129], [130], [135], [136], [137], [138] and [139]. Veryparticular preference is given to [118a], [188b], [119a], [120a],[121a], [126a], [135], [136], [137], [138] and [139]. Many compounds inthis series are produced as “bulk” chemicals.

Epoxidized Fatty Acid Esters and Other Epoxide Compounds

The inventive stabilizer combination may additionally preferablycomprise at least one epoxidized fatty acid ester. Useful for thispurpose are in particular esters of fatty acids from natural sources(fatty acid glycerides), such as soybean oil or rapeseed oil. However,it is also possible to use synthetic products such as epoxidized butyloleate. It is likewise possible to use epoxidized polybutadiene andpolyisoprene, optionally also in partially hydroxylated form, orglycidyl acrylate and glycidyl methacrylate, as a homo- or copolymer.These epoxy compounds may also be applied to an alumino salt compound;on this subject, see also DE 4,031,818 A1.

Liquid or highly viscous glycidyl or epoxide compounds may also beattached to silica- or silicate-containing supports and be used in asolid, non-tacky form.

Phenol Compounds

This category includes phenols and aminophenols, such as resorcinol,resorcinol monomethyl ether, phloroglucinol, 2-naphthol,3-hydroxyaniline and 3-hydroxydiphenylamine.

Inventive stabilizer systems preferably comprise

cyanamide compounds of the formula (E)

-   -   where    -   R⁴ are each independently H, nitrile, carbamoyl, R¹, R², R¹CO,        R²CO, Na, K, Mg_(1/2) and Ca_(1/2) or R₂ ⁴=tetra-, penta- or        hexamethylene, and o=1, 2 or 3.

(E) Monomeric cyanamides: [140] cyanamide and its salts, especially[141] calcium cyanamide, [142] monomethylcyanamide, [143]monoethylcyanamide, [144] monopropylcyanamide, [145] monobutylcyanamide,[146] monopentylcyanamide, [147] monohexylcyanamide, [148]monoheptylcyanamide, [149] monooctylcyanamide, [150] monophenylcyanamideand [151] monobenzylcyanamide, and also [152] monoallylcyanamide.

[153] 1,1-dimethylcyanamide, [154] 1,1-diethylcyanamide, [155]1,1-dipropylcyanamide, [156] 1,1-dibutylcyanamide, [157]1,1-dipentylcyanamide, [158] 1,1-dihexylcyanamide, [159]1,1-diheptylcyanamide, [160] 1,1-dioctylcyanamide, [161]1,1-diphenylcyanamide, and also [162] 1,1-dibenzylcyanamide and [163]1,1-diallylcyanamide.

[164] Acetylcyanamide, [165] propionylcyanamide, [166]butyroylcyanamide, [167] pentanoylcyanamide, [168] hexanoylcyanamide,[169] heptanoylcyanamide, [170] octanoylcyanamide, [171]nonanoylcyanamide, [172] decanoylcyanamide, [173] undecanoylcyanamide,[174] dodecanoylcyanamide, [175] tridecanoylcyanamide, [176]tetradecanoylcyanamide, [177] pentadecanoylcyanamide, [178]hexadecanoylcyanamide, [179] heptadecanoylcyanamide, [180]octadecanoylcyanamide, [181] nonadecanoyl-cyanamide, [182]eicosanoylcyanamide, [183] benzoylcyanamide, and also [184]tetradecyl-cyanamide, [185] hexadecylcyanamide and [186]octadecylcyanamide. Since cyanamides/cyanamide derivatives in the courseof PVC processing tend to decompose under some circumstances,preliminary compounding in a hot mixer is advisable in the case ofreactive representatives.

(E) Dimers: [187] dicyandiamide and its substitution products and saltsthereof. Preference is given to unsubstituted dicyandiamide.

(E) Trimers: melamines/melamine salts, such as [188] melamine, [189]melamine perchlorate, [190] melamine oxalate, [191] melamine sulphate,[192] melamine nitrate, [193] melamine(pyro, poly)phosphate, melamineborate and [194] melamine isocyanurate. Preference is given to [188],[189], [193] and [194].

N-substituted melamines, such as [195] N-monobutylmelamine, [196]N-monooctyl-melamine, [197] N-monodecylmelamine, [198]N-monododecylmelamine, [199] N-mono-tetradecylmelamine, [200]N-monohexadecylmelamine, [201] N-monooctadecylmelamine, [202]N-monophenylmelamine. And also [203] N-monoacetylmelamine, [204]N-mono-propionylmelamine and [205] N-monobutyroylmelamine, [206]N-monophenylmelamine, [207] N-monoallylmelamine and [208]N-monobenzylmelamine, [209] o-hydroxyphenyl-melamine and [210, 211]2-hydroxyethyl(propyl)melamine.

N,N′-substituted melamines, such as [212] N,N′-dibutylmelamine, [213]N,N′-dioctyl-melamine, [214] N,N′-didecylmelamine, [215]N,N′-dihexadecylmelamine, and also [216] N,N′-dioctadecylmelamine and[217, 218] N,N′-bis-2-hydroxyethyl(propyl)melamine.

N,N′,N″-substituted melamines such as [219] N,N′,N″-tributylmelamine,[220] N,N′,N″-trioctylmelamine, [221] N,N′,N″-tridecylmelamine, [222]N,N′,N″-tetradecylmelamine, [223] N,N′,N″-trihexadecylmelamine and [224]N,N′,N″-trioctadecylmelamine, and also [225]N,N′,N″-phenylbis(hydroxyethyl)melamine and [226]N,N′,N″-tris(hydroxyethyl)melamine, [227] N,N′,N″-triacetylmelamine,[228] N,N′,N″-tripropionylmelamine, [229] N,N′,N″-tribenzoylmelamine,and also [230] N,N′,N″-triallylmelamine and [231]N,N′,N″-tribenzyl-melamine, [232] N,N′,N″-triphenylmelamine and [233]N,N′,N″-tricyclohexylmelamine, [234]N,N′,N″-tris(hydroxypropyl)melamine, and [235]N,N′,N″-phenylbis(hydroxypropyl)-melamine.

Preference is given to the substances [141], [142], [143], [144], [150],[151], [153], [154], [155], [159], [162], [163], [164], [176], [178],[184], [185] and [186], [187] and [188]. Also preferred are [206],[207], [208], [209], [210], [211]. Likewise preferred are [217, 218],[226], [227], [228], [229], [230] and [231].

Particular preference is given to [187], [188], [209], [210] and [211].Also particularly preferred are [226], [227], [228], [229], [230] and[231]. Very particular preference is given to [141], [187], [188] and[194] in micronized form (particle size <50 μm).

Likewise is very particularly preferred. the calcium and magnesium saltof [187], [188] or [194] are so-called “commodities”. The calcium andmagnesium salts can also be synthesized “in situ” during the PVCprocessing or beforehand in the course of formulation or compoundingfrom magnesium hydroxide or calcium hydroxide. To lower the meltingpoint of [187], eutectic mixtures with N,N′-disubstituted (thio)ureas oraniline derivatives or with aminobenzenesulphonamides are particularlypreferred.

5. Preferred two-substance or multisubstance combinations of at leastone HCl scavenger (SCV)+at least one booster (A) are*:

[232] CaH(u)⁵⁾ with [A-1], [A-2], [A-3], [A-4] and [A-5]

[233] CaH(c)⁶⁾ with [A-1], [A-2], [A-3], [A-4] and [A-5]

[234] MgH¹¹⁾ with [A-1], [A-2], [A-3], [A-4] and [A-5]

[235] CaAcac¹²⁾ with [A-1], [A-2], [A-3], [A-4] and [A-5]

[236] MgAcac¹³⁾ with [A-1], [A-2], [A-3], [A-4] and [A-5]

[237] CaSt³⁸⁾ with [A-1], [A-2], [A-3], [A-4] and [A-5]

[238] MgSt³⁷⁾ with [A-1], [A-2], [A-3], [A-4] and [A-5]

[239] Hytal⁷⁾ with [A-1], [A-2], [A-3], [A-4] and [A-5]

[240] NaZA¹⁰⁾ with [A-1], [A-2], [A-3], [A-4] and [A-5]

[241] HEXDGE²⁹⁾ with [A-1], [A-2], [A-3], [A-4] and [A-5]

[241a] c-HEXDGE^(29a)) with [A-1], [A-2], [A-3], [A-4] and [A-5]

[242] BADGE²⁵⁾ with [A-1], [A-2], [A-3], [A-4] and [A-5]

[243] BFDGE²⁶⁾ with [A-1], [A-2], [A-3], [A-4] and [A-5]

[244] Glydi³⁰⁾ with [A-1], [A-2], [A-3], [A-4] and [A-5]

[245] Glytri³¹⁾ with [A-1], [A-2], [A-3], [A-4] and [A-5]

[246] ESBO⁵⁷⁾ with [A-1], [A-2], [A-3], [A-4] and [A-5]

[247] DCN²⁰⁾ with [A-1], [A-2], [A-3], [A-4] and [A-5]

[248] Mel²³⁾ with [A-1], [A-2], [A-3], [A-4] and [A-5]

[249] ACEGA²⁴⁾ with [A-1], [A-2], [A-3], [A-4] and [A-5]

[250] TEPC³²⁾ with [A-1], [A-2], [A-3], [A-4] and [A-5]

[251] Cardura³⁵⁾ with [A-1], [A-2], [A-3], [A-4] and [A-5]

very particular preference being given to the combinations in [232],[233], [241], [241a] and [248], in each case with [A-1]. for footnotesand abbreviations, see patent examples, application technology

6. Likewise preferred are three-substance or multisubstance combinationsof at least two different scavengers (SCV) and at least one booster (A):

[232a] CaH(u)⁵⁾ with Mel²³⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[233a] CaH(c)⁶⁾ with Mel²³⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[233b] CaH(c)⁶⁾ with CaSt³⁸⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

very particular preference being given to the combination in [232a] with[A-1].

7. Particular preference is given to three-substance or multisubstancecombinations of at least one initial colour improver (ICI) from compoundclasses (B-1), (B-2), (C-1), (C-2) with at least one scavenger (SCV) andat least one booster (A):

[252] CADMU⁴⁴⁾ with CaH(u)⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[253] CADMU⁴⁴⁾ with CaH(c)⁶⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[254] CADMU⁴⁴⁾ with MgH¹¹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[255] CADMU⁴⁴⁾ with CaAcac¹²⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[256] CADMU⁴⁴⁾ with MgAcac¹³⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[257] CADMU⁴⁴⁾ with CaSt³⁸⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[258] CADMU⁴⁴⁾ with MgSt³⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[259] CADMU⁴⁴⁾ with Hytal⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[260] CADMU⁴⁴⁾ with NaZA¹⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[261] CADMU⁴⁴⁾ with HEXDGE²⁹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[261a] CADMU⁴⁴⁾ with c-HEXDGE^(29a)) and [A-1], [A-2], [A-3], [A-4] and[A-5]

[262] CADMU⁴⁴⁾ with BADGE²⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[263] CADMU⁴⁴⁾ with BFDGE²⁶⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[264] CADMU⁴⁴⁾ with Glydi³⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[265] CADMU⁴⁴⁾ with Glytri³¹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[266] CADMU⁴⁴⁾ with ESBO⁵⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[267] CADMU⁴⁴⁾ with DCN²⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[268] CADMU⁴⁴⁾ with Mel²³⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[269] CADMU⁴⁴⁾ with ACEGA²⁴⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[270] CADMU⁴⁴⁾ with TEPC³²⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[271] CADMU⁴⁴⁾ with Cardura³⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

very particular preference being given to [252], [253], [261], [261a]and [268]. Emphasis is given here to the combinations with [A-1].

[272] DMAU⁴³⁾ with CaH(u)⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[273] DMAU⁴³⁾ with CaH(c)⁶⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[274] DMAU⁴³⁾ with MgH¹¹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[275] DMAU⁴³⁾ with CaAcac¹²⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[276] DMAU⁴³⁾ with MgAcac¹³⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[277] DMAU⁴³⁾ with CaSt³⁸⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[278] DMAU⁴³⁾ with MgSt³⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[279] DMAU⁴³⁾ with Hytal⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[280] DMAU⁴³⁾ with NaZA¹⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[281] DMAU⁴³⁾ with HEXDGE²⁹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[281a] DMAU⁴³⁾ with c-HEXDGE^(29a)) and [A-1], [A-2], [A-3], [A-4] and[A-5]

[282] DMAU⁴³⁾ with BADGE²⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[283] DMAU⁴³⁾ with BFDGE²⁶⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[284] DMAU⁴³⁾ with Glydi³⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[285] DMAU⁴³⁾ with Glytri³¹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[286] DMAU⁴³⁾ with ESBO⁵⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[287] DMAU⁴³⁾ with DCN²⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[288] DMAU⁴³⁾ with Mel²³⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[289] DMAU⁴³⁾ with ACEGA²⁴⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[290] DMAU⁴³⁾ with TEPC³²⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[291] DMAU⁴³⁾ with Cardura³⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

very particular preference being given to [272], [273], [281], [281a]and [288].

Emphasis is given here to the combinations with [A-1].

[292] AC-1⁴¹⁾ with CaH(u)⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[293] AC-1⁴¹⁾ with CaH(c)⁶⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[294] AC-1⁴¹⁾ with MgH¹¹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[295] AC-1⁴¹⁾ with CaAcac¹²⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[296] AC-1⁴¹⁾ with MgAcac¹³⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[297] AC-1⁴¹⁾ with CaSt³⁸⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[298] AC-1⁴¹⁾ with MgSt³⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[299] AC-1⁴¹⁾ with Hytal⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[300] AC-1⁴¹⁾ with NaZA¹⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[301] AC-1⁴¹⁾ with HEXDGE²⁹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[301a] AC-1⁴¹⁾ with c-HEXDGE^(29a)) and [A-1], [A-2], [A-3], [A-4] and[A-5]

[302] AC-1⁴¹⁾ with BADGE²⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[303] AC-1⁴¹⁾ with BFDGE²⁶⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[304] AC-1⁴¹⁾ with Glydi³⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[305] AC-1⁴¹⁾ with Glytri³¹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[306] AC-1⁴¹⁾ with ESBO⁵⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[307] AC-1⁴¹⁾ with DCN²⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[308] AC-1⁴¹⁾ with Mel²³⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[309] AC-1⁴¹⁾ with ACEGA²⁴⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[310] AC-1⁴¹⁾ with TEPC³²⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[311] AC-1⁴¹⁾ with Cardura³⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

very particular preference being given to [292], [293], [301], [301a]and [308].

Emphasis is given here to the combinations with [A-1].

[312] AC-2⁴²⁾ with CaH(u)⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[313] AC-2⁴²⁾ with CaH(c)⁶⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[314] AC-2⁴²⁾ with MgH¹¹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[315] AC-2⁴²⁾ with CaAcac¹²⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[316] AC-2⁴²⁾ with MgAcac¹³⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[317] AC-2⁴²⁾ with CaSt³⁸⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[318] AC-2⁴²⁾ with MgSt³⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[319] AC-2⁴²⁾ with Hytal⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[320] AC-2⁴²⁾ with NaZA¹⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[321] AC-2⁴²⁾ with HEXDGE²⁹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[321a] AC-2⁴²⁾ with c-HEXDGE^(29a)) and [A-1], [A-2], [A-3], [A-4] and[A-5]

[322] AC-2⁴²⁾ with BADGE²⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[323] AC-2⁴²⁾ with BFDGE²⁶⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[324] AC-2⁴²⁾ with Glydi³⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[325] AC-2⁴²⁾ with Glytri³¹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[326] AC-2⁴²⁾ with ESBO⁵⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[327] AC-2⁴²⁾ with DCN²⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[328] AC-2⁴²⁾ with Mel²³⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[329] AC-2⁴²⁾ with ACEGA²⁴⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[330] AC-2⁴²⁾ with TEPC³²⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[331] AC-2⁴²⁾ with Cardura³⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

very particular preference being given to [312], [313], [321], [321a]and [328].

Emphasis is given here to the combinations with [A-1].

[332] M-DHP-1 with CaH(u)⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[333] M-DHP-1⁴⁶⁾ with CaH(c)⁶⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[334] M-DHP-1⁴⁶⁾ with MgH¹¹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[335] M-DHP-1⁴⁶⁾ with CaAcac¹²⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[336] M-DHP-1⁴⁶⁾ with MgAcac¹³⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[337] M-DHP-1⁴⁶⁾ with CaSt¹³⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[338] M-DHP-1⁴⁶⁾ with MgSt³⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[339] M-DHP-1⁴⁶⁾ with Hytal⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[340] M-DHP-1⁴⁶⁾ with NaZA¹⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[341] M-DHP-1⁴⁶⁾ with HEXDGE²⁹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[341a] M-DHP-1⁴⁶⁾ with c-HEXDGE^(29a)) and [A-1], [A-2], [A-3], [A-4]and [A-5]

[342] M-DHP-1⁴⁶⁾ with BADGE²⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[343] M-DHP-1⁴⁶⁾ with BFDGE²⁶⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[344] M-DHP-1⁴⁶⁾ with Glydi³⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[345] M-DHP-1⁴⁶⁾ with Glytri³¹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[346] M-DHP-1⁴⁶⁾ with ESBO⁵⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[347] M-DHP-1⁴⁶⁾ with DCN²⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[348] M-DHP-1⁴⁶⁾ with Mel²³⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[349] M-DHP-1⁴⁶⁾ with ACEGA²⁴⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[350] M-DHP-1⁴⁶⁾ with TEPC³²⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[351] M-DHP-1⁴⁶⁾ with Cardura³⁵⁾ and [A-1], [A-2], [A-3], [A-4] and[A-5]

very particular preference being given to [332], [333], [341], [341a]and [348].

Emphasis is given here to the combinations with [A-1].

[352] M-DHP-2⁴⁷⁾ with CaH(u)⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[353] M-DHP-2⁴⁷⁾ with CaH(c)⁶⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[354] M-DHP-2⁴⁷⁾ with MgH¹¹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[355] M-DHP-2⁴⁷⁾ with CaAcac¹²⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[356] M-DHP-2⁴⁷⁾ with MgAcac¹³⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[357] M-DHP-2⁴⁷⁾ with CaSt³⁸⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[358] M-DHP-2⁴⁷⁾ with MgSt³⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[359] M-DHP-2⁴⁷⁾ with Hytal⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[360] M-DHP-2⁴⁷⁾ with NaZA¹⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[361] M-DHP-2⁴⁷⁾ with HEXDGE²⁹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[361a] M-DHP-2⁴⁷⁾ with c-HEXDGE^(29a)) and [A-1], [A-2], [A-3], [A-4]and [A-5]

[362] M-DHP-2⁴⁷⁾ with BADGE²⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[363] M-DHP-2⁴⁷⁾ with BFDGE²⁶⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[364] M-DHP-2⁴⁷⁾ with Glydi³⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[365] M-DHP-2⁴⁷⁾ with Glytri³¹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[366] M-DHP-2⁴⁷⁾ with ESBO⁵⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[367] M-DHP-2⁴⁷⁾ with DCN²⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[368] M-DHP-2⁴⁷⁾ with Mel²³⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[369] M-DHP-2⁴⁷⁾ with ACEGA²⁴⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[370] M-DHP-2⁴⁷⁾ with TEPC³²⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[371] M-DHP-2⁴⁷⁾ with Cardura³⁵⁾ and [A-1], [A-2], [A-3], [A-4] and[A-5]

very particular preference being given to [352], [353], [361], [361a]and [368].

Emphasis is given here to the combinations with [A-1].

[372] P-DHP⁵⁴⁾ with CaH(u)⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[373] P-DHP⁵⁴⁾ with CaH(c)⁶⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[374] P-DHP⁵⁴⁾ with MgH¹¹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[375] P-DHP⁵⁴⁾ with CaAcac¹²⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[376] P-DHP⁵⁴⁾ with MgAcac¹³⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[377] P-DHP⁵⁴⁾ with CaSt³⁸⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[378] P-DHP⁵⁴⁾ with MgSt³⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[379] P-DHP⁵⁴⁾ with Hytal⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[380] P-DHP⁵⁴⁾ with NaZA¹⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[381] P-DHP⁵⁴) with HEXDGE²⁹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[381a] P-DHP⁵⁴⁾ with c-HEXDGE^(9a)) and [A-1], [A-2], [A-3], [A-4] and[A-5]

[382] P-DHP⁵⁴⁾ with BADGE²⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[383] P-DHP⁵⁴⁾ with BFDGE²⁶⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[384] P-DHP⁵⁴⁾ with Glydi³⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[385] P-DHP⁵⁴⁾ with Glytri³¹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[386] P-DHP⁵⁴⁾ with ESBO⁵⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[387] P-DHP⁵⁴⁾ with DCN²⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[388] P-DHP⁵⁴⁾ with Mel²³⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[389] P-DHP⁵⁴⁾ with ACEGA²⁴⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[390] P-DHP⁵⁴⁾ with TEPC³²⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[391] P-DHP⁵⁴⁾ with Cardura³⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

very particular preference being given to [372], [373], [381], [381a]and [388].

Emphasis is given here to the combinations with [A-1].

[392] Naf⁴⁵⁾ with CaH(u)⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[393] Naf⁴⁵⁾ with CaH(c)⁶⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[394] Naf⁴⁵⁾ with MgH¹¹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[395] Naf⁴⁵⁾ with CaAcac¹²⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[396] Naf⁴⁵⁾ with MgAcac¹³⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[397] Naf⁴⁵⁾ with CaSt³⁸⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[398] Naf⁴⁵⁾ with MgSt³⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[399] Naf⁴⁵⁾ with Hytal⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[400] Naf⁴⁵⁾ with NaZA¹⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[401] Naf⁴⁵⁾ with HEXDGE²⁹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[401a] Naf⁴⁵⁾ with c-HEXDGE^(29a)) and [A-1], [A-2], [A-3], [A-4] and[A-5]

[402] Naf⁴⁵⁾ with BADGE²⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[403] Naf⁴⁵⁾ with BFDGE²⁶⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[404] Naf⁴⁵⁾ with Glydi³⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[405] Naf⁴⁵⁾ with Glytri³¹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[406] Naf⁴⁵⁾ with ESBO⁵⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[407] Naf⁴⁵⁾ with DCN²⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[408] Naf⁴⁵⁾ with Mel²³⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[409] Naf⁴⁵⁾ with ACEGA²⁴⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[410] Naf⁴⁵⁾ with TEPC³²⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[411] Naf⁴⁵⁾ with Cardura³⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

very particular preference being given to [392], [393], [401], [401a]and [408].

Emphasis is given here to the combinations with [A-1].

[412] Hyd⁵⁶⁾ with CaH(u)⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[413] Hyd⁵⁶⁾ with CaH(c)⁶⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[414] Hyd⁵⁶⁾ with MgH¹¹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[415] Hyd⁵⁶⁾ with CaAcac¹²⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[416] Hyd⁵⁶⁾ with MgAcac¹³⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[417] Hyd⁵⁶⁾ with CaSt³⁸⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[418] Hyd⁵⁶⁾ with MgSt³⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[419] Hyd⁵⁶⁾ with Hytal⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[420] Hyd⁵⁶⁾ with NaZA¹⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[421] Hyd⁵⁶⁾ with HEXDGE²⁹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[421a] Hyd⁵⁶) with c-HEXDGE^(29a)) and [A-1], [A-2], [A-3], [A-4] and[A-5]

[422] Hyd⁵⁶⁾ with BADGE²⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[423] Hyd⁵⁶⁾ with BFDGE²⁶⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[424] Hyd⁵⁶⁾ with Glydi³⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[425] Hyd⁵⁶⁾ with Glytri³¹⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[426] Hyd⁵⁶⁾ with ESBO⁵⁷⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[427] Hyd⁵⁶⁾ with DCN²⁰⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[428] Hyd⁵⁶⁾ with Mel²³⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[429] Hyd⁵⁶⁾ with ACEGA²⁴⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[430] Hyd⁵⁶⁾ with TEPC³²⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

[431] Hyd⁵⁶⁾ with Cardura³⁵⁾ and [A-1], [A-2], [A-3], [A-4] and [A-5]

very particular preference being given to [412], [413], [421], [421a]and [428].

Emphasis is given here to the combinations with [A-1].

It will be appreciated that it is also possible to combine one or moreICIs with one or more SCVs and one or more [A]s.

The following combinations of this type, which are very particularlypreferred, are specified:

8. Mixtures of (B-1) with (E)/CaH or CaSt and [A-1]

[432] DMAU⁴³⁾ with Mel²³⁾/CaH(u)⁵⁾ and [A-1]

[433] DMAU⁴³⁾ with Mel²³⁾/CaH(c)⁶⁾ and [A-1]

[434] DMAU⁴³⁾ with Mel²³⁾/CaSt³⁸⁾ and [A-1]

or

[435] M-DHP-2⁴⁷⁾ with HEXDGE²⁹⁾/c-HEXDGE^(29a)) and [A-1]

In flexible PVC, combinations of TEAP with 1,4-cyclohexanedimethanoldiglycidyl ether [118b] are very particularly preferred. Veryparticularly suitable initial colour improvers here are aminocrotonicesters and dihydropyridines.

Use of (A) as an Antistat or Antistat Component (AS)

EP 0 751 179 A1 describes alkali metal perchlorates and triflates asantistat components. They function in the presence of polyglycolmono-fatty acid esters. One disadvantage is the limited solubility ofthese salts in the esters mentioned. It has been found that,surprisingly, the inventive inner complexes (A) have a very goodsolubility herein and display good antistatic properties.

Polymer substrates of this type include: rigid PVC, flexible PVC,semirigid PVC, CPVC, CPE, PVDC, HDPE, LDPE, PP, PS, HIPS, PU, PA, PC,PET, PBT, TPU, PMMA, PVA, ABS, SAN, MBS, MABS, NBR, NAR, EVA, ASA, andEPDM.

Additive components to (A) used here are the following systems:

glyceryl ether and/or ester, R⁸OCH₂CH(OH)CH₂OH or R⁸CO₂CH₂CH(OH)CH₂OHand/or a DEA derivative R⁹—[C(O)]_(d)—N(C₂H₄OH)₂ orR⁸OCH₂CH(OH)CH₂—[C(O)]_(d)—N(C₂H₄OH)₂ orR⁹N((CH₂)₂)OH)—(CH₂)₃—[C(O)]_(d)—N(C₂H₄OH)₂ and/or a paraffinsulphate(or -sulphonate) salt C₁₂-C₁₈-alkyl-(O)_(d′)—SO₃Na, Li, K and/or apolyoxyalkylene of the formula (F)

R⁸—O—[CH(R¹⁰)—CH₂—O—]_(a)—[CH₂—[CH(OH)]_(b)—CH₂—O]_(c)[C(O)]_(d″)—R⁹  (F)

-   where-   each R⁸ is independently H, C₁-C₂₄-alkyl, C₂-C₂₄-alkenyl,    CH₂═CH—C(O) or CH₂═CCH₃—C(O);-   each R⁹ is independently C₁-C₂₄-alkyl, C₂-C₂₄-alkenyl, (CH₂)₂OH,    CH₂—COOH or N(C₁-C₈-alkyl)₃Hal;-   R¹⁰=H or CH₃,-   Hal=Cl, Br or I;-   a=an integer greater than or equal to 2,-   b=an integer of 1 to 6, and-   c, d, d′, d″ are each independently 0 or 1.

When substituents in the compounds of the formula (F) are alkyl having 1to 24 carbon atoms, useful radicals therefor are those such as methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl andtetracosyl, and corresponding branched isomers.

When substituents in the compounds of the formula (F) are alkenyl havingfrom 1 to 24 carbon atoms, these radicals derive from the alkyl radicalsmentioned, the double bond preferably being arranged in the middle ofthe hydrocarbon chain. A particularly preferred alkenyl radical isoleyl. When d is 1, R⁹ as alkenyl is preferably also CH₂═CH— orCH₂═CCH₃—.

In the compounds of the formula (F), R⁸ is preferably H or C₁-C₄-alkyland most preferably H.

In the compounds of the formula (F), R⁹ is preferably C₆-C₂₀-alkyl,C₆-C₂₀-alkenyl or N(C₁-C₈-alkyl)₃Cl, and most preferably C₆-C₂₀-alkyl orC₆-C₂₀-alkenyl.

In the compounds of the formula (F), Hal is preferably Cl.

In the compounds of the formula (F), a is preferably a number from 2 to20 and most preferably a number from 2 to 14.

In the compounds of the formula (F), b is preferably a number from 2 to6 and most preferably the number 4.

In the compounds of the formula (F), c is preferably the number 0 or 1and, most preferably, c is the number 0 and d is the number 1.

Particular preference is given to polypropylene glycol lauryl ester,polypropylene glycol oleyl ester, polypropylene glycolmethyldiethylammonium chloride, polyethylene glycol monomethyl ether,polyethylene glycol lauryl ester, polyethylene glycol oleyl ester,polyethylene glycol oleyl ether, polyethylene glycol sorbitan monolaurylester, polyethylene glycol stearyl ester, polyethylene glycolpolypropylene glycol lauryl ether and polyethylene glycol lauryl ethercarboxylic acid.

Very particular preference is given to polyethylene glycol oleyl etherand especially to polyethylene glycol lauryl ester.

Very particular preference is given to compounds of the formula (F) inwhich R⁸═H, R⁹═C₆-C₂₀-alkenyl, R¹⁰═H or CH₃, a is a number from 2 to 14,c is zero and d is one.

Examples thereof are glycerol monolauryl, monooleyl, monopalmityl andmonostearyl ether; glycerol monolaurate, monooleate, monopalmitate andmonostearate; lauryl-, oleyl-, palmityl- and stearyldiethanolamine;polyethylene glycol (PEG) monolaurate, monooleate, monopalmitate andmonostearate, PEG monolauryl, monomyristyl, monopalmityl, monostearyland monooleyl ether. Oleic diethanolamide, palmitic diethanolamide andstearic diethanolamide. Sodium tetra-, hexa- and octadecanesulphonate or-sulphate, potassium tetra-, hexa- and octadecanesulphonate or-sulphate, lithium tetra-, hexa- and octadecanesulphonate or -sulphate.

Commercial products include: DEHYDAT®10, DEHYDAT®R80X, IRGASTAT® P,ATMER™, Lankrostat® LA3, Ethoduomeen® T/12, Ethomeen® HT/12, Ethomeen®T/12, Ethomeen® O/12, Ethomeen® C/12, TEGIN® R90 and NOROPLAST® 2000.

Further important additives for improving performance are phosphites andsterically hindered amines.

Phosphites

Organic phosphites are known costabilizers for chlorinated polymers.Examples are trioctyl phosphite, tridecyl phosphite, tridodecylphosphite, tritridecyl phosphite, tripentadecyl phosphite, trioleylphosphite, tristearyl phosphite, triphenyl phosphite, trilaurylphosphite, tricresyl phosphite, tris(nonylphenyl)phosphite,tris(2,4-t-butylphenyl)phosphite or tricyclohexyl phosphite. Furthersuitable phosphites are various mixed aryl dialkyl phosphites or alkyldiaryl phosphites, such as phenyl dioctyl phosphite, phenyl didecylphosphite, phenyl didodecyl phosphite, phenyl ditridecyl phosphite,phenyl ditetradecyl phosphite, phenyl dipentadecyl phosphite, octyldiphenyl phosphite, decyl diphenyl phosphite, undecyl diphenylphosphite, dodecyl diphenyl phosphite, tridecyl diphenyl phosphite,tetradecyl diphenyl phosphite, pentadecyl diphenyl phosphite, oleyldiphenyl phosphite, stearyl diphenyl phosphite and dodecylbis(2,4-di-tert-butylphenyl)phosphite. In addition, it is alsoadvantageously possible to use phosphites of different di- or polyols,for example tetraphenyl dipropylene glycol diphosphite, poly(dipropyleneglycol) phenyl phosphite, tetra(isodecyl) dipropylene glycoldiphosphite, tris(dipropylene glycol) phosphite,tetramethylolcyclohexanol decyl diphosphite, tetramethylolcyclohexanolbutoxy ethoxy ethyl diphosphite, tetramethylolcyclohexanol nonylphenyldiphosphite, bis(nonyl)phenyl di(trimethylolpropane) diphosphite,bis(2-butoxyethyl) di(trimethylolpropane) diphosphite, trishydroxyethylisocyanurate hexadecyl triphosphite, didecylpentaerythritol diphosphite,distearylpentaerythritol diphosphite,bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, and mixtures ofthese phosphites and aryl/alkyl phosphite mixtures of the statisticalcomposition (H₁₉C₉-C₆H₄)O_(1.5)P(OC_(12.13)H_(25.27))_(1.5) or(C₈H₁₇—C₆H₄—O—)₂P(i-C₈H₁₇O),(H₁₉C₉-C₆H₄)O_(1.5)P(OC_(9.11)H_(19.23))_(1.5).Industrial examples are Naugard P, Mark CH300, Mark CH301, Mark CH302and Mark CH55 (manufacturer: Crompton Corp. USA). The organic phosphitesmay be employed in an amount of, for example, 0.01 to 10 parts byweight, appropriately 0.05 to 5 parts by weight and especially 0.1 to 3parts by weight, based on 100 parts by weight of PVC.

Sterically Hindered Amines (HALS)

The sterically hindered amines are generally compounds containing thegroup

-   -   in which A and V are each independently C₁₋₈-alkyl,        C₃₋₈-alkenyl, C₅₋₈-cycloalkyl or C₇₋₉-phenylalkyl, or together        form C₂₋₅-alkylene optionally interrupted by O, NH or CH₃—N, or        are a cyclic sterically hindered amine, especially a compound        from the group of the alkyl- or polyalkylpiperidines, in        particular of the tetramethylpiperidines containing the group

Examples of such polyalkylpiperidine compounds are as follows (in theoligomeric or polymeric compounds, n and r are in the range of 2-200,preferably in the range of 2-10, especially 3-7):

-   01)    N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)ethylene-1,2-diacetamide-   01a)    N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylene-1,6-diacetamide-   01b)    N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)ethylene-1,2-diformamide-   02) N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)adipamide-   03) N,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)oxamide-   04) 4-hydroxybenzamido-2,2,6,6-tetramethylpiperidine

Also useful are compounds of the following structure (G-3):

Examples of compounds of the formula (G-3) are:

No

42) PMP-NH— H₂N— H₂N— 43) TMP-NH— TMP-NH— H₂N— 44) TMP-NH— Me₂N— Me₂N—45) TMP-NH— TMP-NH— TMP-NBu- 46) TMP-NH— TMP-NH— (HO—CH₂CH₂—)₂N— 47)TMP-NH— (HO—CH₂CH₂—)NH— TMP-NBu- 48) (TMP)₂-N— H₂N— H₂N— 49) TMP-NH—

50) (TMP)₂N— (TMP)₂N— (TMP)₂N— 51) PMP-NH— PMP-NH— PMP-NH— 52)(i-Pr)₂N—C₂H₄—N(TMP)- Pr₂N— Pr₂N— 53) (i-Pr)₂N—C₂H₄—N(TMP)- TMP-NHTMP-NH 54) TMP-NH— Et₂N— TMP-NH— 55) TMP-NH— (HOCH₂)₃C—NH— TMP-NH— 56)TMP-NH—

Et₂N—C₂H₄—NH— 57) TMP₂N— TMP-NH— Et₂N—C₂H₄—NH— 58) TMP-NH— TMP-NH—

59) TMP-NH—

TMP-NH— 60) TMP-NH—

61) TMP-NH— Et₂N—C₂H₄—NH—

62) TMP-N(nBu)- Et₂N— Et₂N— 63) TMP-N(Et)— (n-Bu)₂N— TMP-N(Et)— 64)TMP-NH—

TMP-NH— 65) TMP-NH—

TMP-NH— 66)

67)

68)

TMP-NH— TMP-NH— 69) TMP-NH— (HO—C₂H₄)₂N— (HO—C₂H₄)₂N— 70)

TMP-NH— TMP-NH— 71)

PMP-NH— PMP-NH— 72)

73)

H₂N— H₂N— 74)

TMP-NH— TMP-NH— 75)

76)

TMP-NH— TMP-NH— 77)

78)

TMP-NH— TMP-NH— 79)

(i-Pr)₂N—C₂H₄—NH— (i-Pr)₂N—C₂H₄—NH— 80)

Et₂N— Et₂N— 81)

Bu₂N— Bu₂N— 82)

TMP-NH— TMP-NH— 83)

TMP-NH— Et₂N—C₂H₄—NH— 84) (TMP₂)N— (i-Pr)₂N—C₂H₄—NH— (i-Pr)₂N—C₂H₄—NH—85) TMPNH— Et₂N—C₂H₄—NH— Et₂N—C₂H₄—NH— 86)

TMP-N(nBu)- TMP-N(nBu)-

Explanations:

Me=methyl;

Et=ethyl; Pr=propyl; Bu=butyl.

Further useful compounds are:

Polymer formed from:

Further examples are:

and also compounds of the structure (G-4)

Examples of compounds of the formula (G-4) are:

No AYN—CHR₁ ^(#))_(m)—NR₅ ^(#)— R₆ ^(#)R₇ ^(#)N— R₈ ^(#)R₉ ^(#)N— 140Et₂N—C₂H₄—NH— —NH₂ —NH₂ 141 Et₂N—C₂H₄—NH— Et₂N—C₂H₄—NH— Et₂N—C₂H₄—NH—142 ^(n)Pr₂N—C₃H₆—NH— HO—C₂H₄NH— HO—C₂H₄—NH— 143 ^(n)Pr₂N—C₂H₄—NH—(HO—C₂H₄)₂N— (HO—C₂H₄)₂N— 144

Et—NH—

145

146

147

148 ^(iso)Pr₂N—C₂H₄—NH— ^(iso)Pr₂N—C₂H₄—NH— ^(iso)Pr₂N— 149^(iso)Pr₂N—C₂H₄—NH— ^(iso)Pr₂N—C₂H₄—NH— ^(iso)PrNEt— 150 Et₂N—C₂H₄—NH—Et₂N—C₂H₄—NH—

In this table, Me = methyl, Bu = butyl, ^(tert)Bu = tertiary butyl,^(iso)Pr = isopropyl, ^(n)Pr = normal propyl, Ac = acetyland also NOR-HALS compounds having the group

such as

where R′=CH₃, n-C₄H₉ or c-C₆H₁₁

where R′=CH₃, n-C₄H₉ or c-C₆H₁₁

where R′=CH₃, n-C₄H₉ or c-C₆H₁₁

where R′=CH₃, n-C₄H₉ or c-C₆H₁₁

where R′=CH₃, n-C₄H₉ or c-C₆H₁₁

156) TINUVIN® NOR 371FF

157) TINUVIN® XT 833

158) TINUVIN® XT 850

Preference is given to triazine-based NOR-HALS compounds.

Also preferred are the compounds 1, 1a, 1b, 3, 4, 6, 9, 16, 41, 87, 88,91, 92, 93, 103, 106, and 111.

Particular preference is given to 1, 1b, 2, 6, 9, 16, 41, 87, 88, 92,93, 103, 111, 151, 152, 153, 154, 155 and 156, 157, 158.

Very particular preference is given to 41, 87, 93, 103, 151, 152, 154,156 and 157.

For stabilization in the chlorinated polymer, the compounds ofcomponents (G-1)-(G-5) are used appropriately in an amount of 0.01 to 10parts, preferably of 0.05 to 5 parts, especially of 0.1 to 3 parts for100 parts of polymer.

Instead of an individual sterically hindered amine, it is also possiblein the context of the present invention to use a mixture of differentsterically hindered amines.

The amines mentioned are frequently known compounds; many of them arecommercially available. The compounds may be present in the polymer toan extent of 0.005 to 5%, preferably to an extent of 0.01 to 2% andespecially to an extent of 0.01 to 1%.

The invention preferably further provides mixtures of glycidyl compound(D) or cyanamide (E)—especially melamine—with at least one stabilizercomponent (A), with at least one further cocomponent (B-1), (B-2), (C-1)and (C-2) to which an HCl scavenger, preferably coated or uncoatedcalcium hydroxide, and optionally a further cocomponent (G-1) or (G-2)or an antistat component (F) is additionally added. Alternativelypreferred are also systems which comprise (A) and scavengers. Thesesystems serve in particular for basis stabilization. Further additivescan be added to these blends.

Preferred further component groups are polyols and disaccharidealcohols, β-diketones, thiophosphites and thiophosphates,mercaptocarboxylic esters, metal hydroxycarboxylate salts, fillers,lubricants, plasticizers, pigments, antioxidants, UV absorbers, lightstabilizers, optical brighteners, blowing agents, antistats, biocides(antimicrobicides), antifogging agents, impact modifiers, processingaids, gelling agents, flame retardants, metal deactivators andcompatibilizers.

It is also possible for further additives such as adhesives, calenderingaids, mould (release agents), lubricants, and also fragrances andcolorants to be present. Examples of such additional components arelisted and explained below (cf. “Handbook of PVC-Formulating” by E. J.Wickson, John Wiley & Sons, New York 1993).

Polyols and Sugar Alcohols

Useful compounds of this type include, for example: pentaerythritol,dipentaerythritol, tripentaerythritol, trimethylolethane,bistrimethylolpropane, inositol, polyvinyl alcohol,bistrimethylolethane, trimethylolpropane, sorbitol, maltitol,isomaltitol, lycasin, mannitol, lactose, leucrose,tris(hydroxyethyl)isocyanurate, palatinitol, tetramethylcyclohexanol,tetramethylolcyclopentanol, tetramethylolpyranol, glycerol, diglycerol,polyglycerol, thiodiglycerol or 1-O-α-D-glycopyranosyl-D-mannitoldihydrate. Preference is given to disaccharide alcohols. Use is alsofound by polyol syrups such as sorbitol syrup, mannitol syrup andmaltitol syrup. The polyols may be employed in an amount of, forexample, 0.01 to 20 parts, appropriately of 0.1 to 20 parts andespecially of 0.1 to 10 parts by weight, based on 100 parts by weight ofPVC.

β-Diketones

Useable 1,3-dicarbonyl compounds are linear or cyclic dicarbonylcompounds. Preference is given to using dicarbonyl compounds of theformula R′₁COCHR′₂—COR′₃ in which R′₁ is C₁-C₂₂-alkyl,C₅-C₁₀-hydroxyalkyl, C₂-C₁₈-alkenyl, phenyl, OH—, C₁-C₄-alkyl-,C₁-C₄-alkoxy- or halogen-substituted phenyl, C₇-C₁₀-phenylalkyl,C₅-C₁₂-cycloalkyl, C₁-C₄-alkyl-substituted C₅-C₁₂-cycloalkyl, or a—R′₅—S—R′₆ or —R′₅—O—R′₆ group; R′₂ is hydrogen, C₁-C₈-alkyl,C₂-C₁₂-alkenyl, phenyl, C₇-C₁₂-alkylphenyl, C₇-C₁₀-phenylalkyl, or a—CO—R′₄ group; R′₃ has one of the definitions given for R′₁ or isC₁-C₁₈-alkoxy, R′₄ is C₁-C₄-alkyl or phenyl; R′₅ is C₁-C₁₀-alkylene, andR′₆ is C₁-C₁₂-alkyl, phenyl, C₇-C₁₈-alkylphenyl or C₇-C₁₀-phenylalkyl.

These include the diketones containing hydroxyl groups PS-EP 0,346,279A1 and the oxa- and thiadiketones in PS-EP 0,307,358 A1, and equally theketoesters based on isocyanic acid in PS-U.S. Pat. No. 4,339,383.

R′₁ and R′₃ as alkyl may especially be C₁-C₁₈-alkyl, e.g. methyl, ethyl,n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl,decyl, dodecyl or octadecyl. R′₁ and R′₃ as hydroxyalkyl are especiallya —(CH₂)_(n)—OH group in which n is 5, 6 or 7.

R′₁ and R′₂ as alkenyl may, for example, be vinyl, allyl, methallyl,1-butenyl, 1-hexenyl or oleyl, preferably allyl.

R′₁ and R′₃ as OH—, alkyl-, alkoxy- or halogen-substituted phenyl may,for example, be tolyl, xylyl, tert-butylphenyl, methoxyphenyl,ethoxyphenyl, hydroxyphenyl, chlorophenyl or dichlorophenyl.

R′₁ and R′₃ as phenylalkyl are especially benzyl. R′₂ and R′₃ ascycloalkyl or alkylcycloalkyl are especially cyclohexyl ormethylcyclohexyl.

R′₂ as alkyl may especially be C₁-C₄-alkyl. R′₂ as C₂-C₁₂-alkenyl mayespecially be allyl. R′₂ as alkylphenyl may especially be tolyl. R′₂ asphenylalkyl may especially be benzyl. R′₂ is preferably hydrogen. R′₃ asalkoxy may, for example, be methoxy, ethoxy, butoxy, hexyloxy, octyloxy,dodecyloxy, tridecyloxy, tetradecyloxy or octadecyloxy. R′₅ asC₁-C₁₀-alkylene is especially C₂-C₄-alkylene. R′₆ as alkyl is especiallyC₄-C₁₂-alkyl, e.g. butyl, hexyl, octyl, decyl or dodecyl.

R′₆ as alkylphenyl is especially tolyl. R′₆ as phenylalkyl is especiallybenzyl.

Examples of 1,3-dicarbonyl compounds of the above general formula andthe alkali metal, alkaline metal and zinc chelates thereof, areacetylacetone, butanoylacetone, heptanoylacetone, stearoylacetone,palmitoylacetone, lauroylacetone, 7-tert-nonylthio-2,4-heptanedione,benzoylacetone, dibenzoylmethane, lauroylbenzoylmethane,palmitoylbenzoylmethane, stearoylbenzoylmethane, isooctylbenzoylmethane,5-hydroxy-capronylbenzoylmethane, tribenzoylmethane,bis(4-methylbenzoyl)methane, benzoyl-p-chlorobenzoylmethane,bis(2-hydroxybenzoyl)methane, 4-methoxybenzoylbenzoylmethane,bis(4-methoxybenzoyl)methane, 1-benzoyl-1-acetylnonane,benzoylacetylphenylmethane, stearoyl-4-methoxybenzoylmethane,bis(4-tert-butylbenzoyl)methane, benzoylformyl-methane,benzoylphenylacetylmethane, bis(cyclohexanoyl)methane,di(pivaloyl)methane, 2-acetylcyclopentanone, 2-benzoylcyclopentanone,methyl, ethyl and allyl diacetoacetate, methyl and ethylbenzoylacetoacetate, methyl and ethyl propionylacetoacetate, and methyland ethyl butyrylacetoacetate, triacetylmethane, methyl, ethyl, hexyl,octyl, dodecyl or octadecyl acetoacetate, methyl, ethyl, butyl,2-ethylhexyl, dodecyl or octadecyl benzoylacetate, and C₁-C₁₈-alkylpropionyl- and butyrylacetates. Ethyl, propyl, butyl, hexyl or octylstearoyl acetates, and also polycyclic β-keto esters as described inPS-EP-A 0 433 230, and dehydroacetic acid and the zinc, magnesium oralkali metal salts thereof. Preference is given to calcium, magnesiumand zinc salts of acetylacetone and of dehydroacetic acid.

Particular preference is given to 1,3-diketo compounds of the aboveformula in which R′₁ is C₁-C₁₈-alkyl, phenyl, OH—, methyl- ormethoxy-substituted phenyl, C₇-C₁₀-phenylalkyl or cyclohexyl, R′₂ ishydrogen, and R′₃ has one of the definitions given for R′¹. Theselikewise include heterocyclic 2,4-diones such asN-phenyl-3-acetylpyrrolidine-2,4-dione. Further representatives of thiscategory are described in PS-EP 0,734,414 A1. The 1,3-diketo compoundsmay be employed in an amount of, for example, 0.01 to 10 parts,appropriately 0.01 to 3 parts and especially 0.01 to 2 parts by weight,based on 100 parts by weight of PVC.

Thiophosphites and Thiophosphates

Thiophosphites and thiophosphates are understood to mean compounds ofthe general type (RS)₃P, (RS)₃P═O or (RS)₃P═S, as described in thepublications PS-DE 28,09,492 A1, EP 0,090,770 A1 and EP 0,573,394 A1.Examples of these compounds are trithiohexyl phosphite, trithiooctylphosphite, trithiolauryl phosphite, trithiobenzyl phosphite,tris(carbo-i-octyloxy)methyl trithiophosphite,tris(carbotrimethylcyclohexyloxy)methyl trithiophosphite,S,S,S-tris(carbo-i-octyloxy)methyl trithiophosphate,S,S,S-tris(carbo-2-ethylhexyloxy)methyl trithiophosphate,S,S,S-tris-1-(carbohexyloxy)ethyl trithiophosphate,S,S,S-tris-1-(carbo-2-ethylhexyloxy)ethyl trithiophosphate,S,S,S-tris-2-(carbo-2-ethylhexyloxy)ethyl trithiophosphate.

Mercaptocarboxylic Esters

Examples of these compounds are esters of thioglycolic acid, thiomalicacid, mercaptopropionic acid, of the mercaptobenzoic acids or ofthiolactic acid, mercaptoethyl stearate and oleate, as described inpublications PS-FR-A 2,459,816, EP 0,090,748 A1, FR-A 2,552,440 and EP0,365,483 A1. The mercaptocarboxylic esters also include polyol estersor the partial esters thereof.

Metal Hydroxycarboxylate Salts

In addition, metal hydroxycarboxylate salts may be present, and themetal may be an alkali metal or alkaline earth metal or aluminium.Preference is given to sodium, potassium, magnesium or calcium. Thehydroxycarboxylic acid may be glycolic acid, lactic acid, malic acid,tartaric acid or citric acid or salicylic acid or 4-hydroxybenzoic acid,or else glyceric acid, gluconic acid and sugar acid (see, for example,PS-GB 1,694,873 and EP 303,564 A1).

Furthermore, other sheet lattice compounds such as lithium hydrotalcitemay be used. Further remarks on this subject can be found in PS-EP0,930,332 A1. The synthesis of L-CAM perchlorate is described, forexample, in PS-EP 0,761,756 A1.

Fillers

For example, calcium carbonate, dolomite, wollastonite, magnesium oxide,magnesium hydroxide, silicates, china clay, talc, glass fibres, glassbeads, woodmeal, mica, metal oxides or metal hydroxides, carbon black,graphite, rock flour, barite, glass fibres, talc, kaolin and chalk areused. Preference is given to chalk (including coated chalk) (HANDBOOK OFPVC FORMULATING E. J. Wickson, John Wiley & Sons, 1993, pp. 393-449) andreinforcing agents (TASCHENBUCH DER KUNSTSTOFFADDITIVE, R. Gächter & H.Müller, Carl Hanser, 1990, p. 549-615).

The fillers may be used in an amount of preferably at least 1 part, forexample 5 to 200 parts, appropriately 5 to 150 parts and especially 5 to100 parts by weight, based on 100 parts by weight of PVC.

Lubricants

Useful lubricants include, for example: montan waxes, fatty acid esters,PE and PP waxes, amide waxes, chloroparaffins, glycerol esters oralkaline earth metal soaps, and also fatty ketones and combinationsthereof, as detailed in PS-EP 0,259,783 A1. Preference is given tocalcium stearate.

Plasticizers

Useful organic plasticizers include, for example, those from thefollowing groups:

(i) phthalic esters, such as preferably di-2-ethylhexyl phthalate,diisononyl phthalate and diisodecyl phthalate, which are also known bythe common abbreviations DOP (dioctyl phthalate, di-2-ethylhexylphthalate), DINP (diisononyl phthalate), DIDP (diisodecyl phthalate)(ii) esters of aliphatic dicarboxylic acids, especially esters of adipicacid, azelaic acid and sebacic acid, preferably di-2-ethylhexyl adipateand diisooctyl adipate(iii) trimellitic esters, for example tri-2-ethylhexyl trimellitate,triisodecyl trimellitate (mixture), triisotridecyl trimellitate,triisooctyl trimellitate (mixture), and also tri-C₆-C₈-alkyl,tri-C₆-C₁₀-alkyl, tri-C₇-C₉-alkyl and tri-C₉-C₁₁-alkyl trimellitate;common abbreviations are TOTM (trioctyl trimellitate, tri-2-ethylhexyltrimellitate), TIDTM (triisodecyl trimellitate) and TITDTM(triisotridecyl trimellitate)(iv) epoxy plasticizers; these are mainly epoxidized unsaturated fattyacids, e.g. epoxidized soyabean oil(v) polymer plasticizers: the most common starting materials for theirpreparation are dicarboxylic acids such as adipic acid, phthalic acid,azelaic acid and sebacic acid; diols such as 1,2-propanediol,1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol anddiethylene glycol, (see ADMEX® types from Velsicol Corp. and PX-811 fromAsahi Denka)(vi) phosphoric esters: a definition of these esters can be found in theaforementioned “TASCHENBUCH DER KUNSTSTOFFADDITIVE” Chapter 5.9.5, pp.408-412. Examples of such phosphoric esters are tributyl phosphate,tri-2-ethylbutyl phosphate, tri-2-ethylhexyl phosphate, trichloroethylphosphate, 2-ethylhexyl diphenyl phosphate, cresyl diphenyl phosphate,triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate;preference is given to tri-2-ethylhexyl phosphate and to Reofos® 50 and95 (Ciba Spezialitätenchemie)(vii) chlorinated hydrocarbons (paraffins)(viii) hydrocarbons(ix) monoesters, e.g. butyl oleate, phenoxyethyl oleate,tetrahydrofurfuryl oleate and alkylsulphonic esters(x) glycol esters, e.g. diglycol benzoates(xi) citric esters, e.g. tributyl citrate and acetyltributyl citrate, asdescribed in PS-WO 02/05206(xii) perhydrophthalic, -isophthalic and -terephthalic esters, and alsoperhydroglycol and—diglycol benzoates; preference is given toperhydrodiisononyl phthalate (Hexamoll® DINCH—manufacturer: BASF), asdescribed in PS-DE 197,56,913 A1, DE 199,27,977 A1, DE 199,27,978 A1 andDE 199,27,979 A1.(xiii) castor oil-based plasticizers (Soft-N-Safe®, manufacturer:DANISCO)(xiv) ketone-ethylene-ester terpolymers Elvaloy® KEE, (Elvaloy® 741,Elvaloy® 742, manufacturer: DuPont).

A definition of these plasticizers and examples thereof are given in“TASCHENBUCH DER KUNSTSTOFFADDITIVE”, R. Gä chter/H. Müller, Carl HanserVerlag, 3rd Ed., 1989, Chapter 5.9.6, pages 412-415, and in “PVCTECHNOLOGY”, W. V. Titow, 4th Ed., Elsevier Publ., 1984, pages 165-170.It is also possible to use mixtures of different plasticizers. Theplasticizers may be employed in an amount of, for example, 5 to 50 partsby weight, appropriately 10 to 45 parts by weight, based on 100 parts byweight of PVC. Rigid PVC or semirigid PVC contains preferably up to 20%,more preferably up to 5% or no plasticizer.

Pigments

Suitable substances are known to those skilled in the art. Examples ofinorganic pigments are TiO₂, zirconium oxide-based pigments, BaSO₄, zincoxide (zinc white) and lithopone (zinc sulphide/barium sulphate), carbonblack, carbon black-titanium dioxide mixtures, iron oxide pigments,Sb₂O₃, (Ti,Ba,Sb)O₂, Cr₂O₃, spinels such as cobalt blue and cobaltgreen, Cd(S,Se), ultramarine blue. Organic pigments are, for example,azo pigments, phthalocyanine pigments, quinacridone pigments, perylenepigments, diketopyrrolopyrrole pigments and anthraquinone pigments.Preference is given to TiO₂, also in micronized form. A definition andfurther descriptions can be found in “HANDBOOK OF PVC FORMULATING”, E.J. Wickson, John Wiley & Sons, New York, 1993.

Antioxidants

These include sterically hindered phenols such as alkylated monophenols,e.g. 2,6-di-tert-butyl-4-methylphenol, alkylthiomethylphenols, e.g.2,4-dioctylthiomethyl-6-tert-butylphenol, alkylated hydroquinones, e.g.2,6-di-tert-butyl-4-methoxyphenol, hydroxylated thiodiphenyl ethers,e.g. 2,2′-thiobis(6-tert-butyl-4-methylphenol), alkylidenebisphenols,e.g. 2,2′-methylenebis(6-tert-butyl-4-methylphenol), benzyl compounds,e.g. 3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether,hydroxybenzylated malonates, e.g. dioctadecyl2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, hydroxybenzylaromatics, e.g.1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,triazine compounds, e.g.2,4-bisoctyl-mercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,phosphonates and phosphonites, e.g. dimethyl2,5-di-tert-butyl-4-hydroxybenzylphosphonate, acylaminophenols, e.g.4-hydroxylauranilide, esters ofbeta(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, ofbeta-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid, ofbeta-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid, esters of3,5-di-tert-butyl-4-hydroxyphenylacetic acid with mono- or polyhydricalcohols, amides of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)propionicacid, e.g.N,N′-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine,vitamin E (tocopherol) and derivatives, and also D,L-ascorbic acid. Theantioxidants may be employed in an amount of, for example, 0.01 to 10parts by weight, appropriately 0.1 to 10 parts by weight and especially0.1 to 5 parts by weight, based on 100 parts by weight of PVC.

UV Absorbers and Light Stabilizers

Examples thereof are benzotriazole derivatives, for example2-(2′-hydroxyphenyl)-1,2,3-benzotriazoles, e.g.2-(2′-hydroxy-5′-methylphenyl)benzotriazole,2-(2′-hydroxy-5′-methylphenyl)-5-methylbenzotriazole,2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)benzotriazole,2-(2′-hydroxy-3′,5′-di-tert-butylphenyl)-5-chlorobenzotriazole. Furtherexamples are 2-hydroxybenzophenones, esters of optionally substitutedbenzoic acids, e.g. 4-tert-butylphenyl salicylate, phenyl salicylate,acrylates, nickel compounds, oxalamides, e.g. 4,4′-dioctyloxyoxanilide,2,2′-dioctyloxy-5,5′-di-tert-butyloxanilide,2-(2-hydroxyphenyl)-1,3,5-triazines, e.g.2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,sterically hindered amines based on tetramethylpiperidine ortetramethylpiperazinone or tetramethylmorpholinone, e.g.bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate,bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate, and also benzoxazinonessuch as 1,4-bis(benzoxazinonyl)benzene.

Optical Brighteners

Examples thereof are bis-1,4-benzoxazoles, phenylcoumarins andbisstyrylbiphenyls, such as 4-methyl-7-diethylaminocoumarin,3-phenyl-7-(4-methyl-6-butoxybenzoxazole)coumarin,4,4′-bis(benzoxazol-2-yl)stilbene and1,4-bis(benzoxazol-2-yl)naphthalene. Preference is given to solutions ofoptical brighteners in a plasticizer, for example DOP.

Blowing Agents

Blowing agents are, for example, organic azo and hydrazo compounds,tetrazoles, oxazines, isatoic anhydride, N-methylisatoic anhydride, andalso soda and sodium bicarbonate. Preference is given toazodicarbonamide and sodium bicarbonate, and to mixtures thereof. Veryparticular preference is given to isatoic anhydride or N-methylisatoicanydride, especially in flexible PVC or semirigid PVC.

Antistats

Antistats are divided into nonionic(a), anionic(b), cationic(c) andamphoteric(d) classes. (a) includes fatty acid ethoxylates, fatty acidesters, ethoxylated fatty alkylamines, fatty acid diethanolamides andethoxylated phenols and alcohols, and also polyglycol monofatty acidesters. (b) includes alkali metal fatty alkanesulphonates and phosphoricacid bis(fatty alcohol ester) alkali metal salts. (c) includesquaternary fatty alkylammonium salts, and (d) includes fatty alkylbetaines and fatty alkyl imidazolinebetaines. Individual preferredcompounds are lauric diethanolamide, myristyldiethanolamine, sodiumoctadecylsulphonate and sodium bis(octadecylphosphate). The presence ofcomponent (A), in many cases, owing to the inherent properties, permitsa reduction in the amount of expensive antistats used.

Definitions and examples of further additives such as impact modifiersand processing aids, gelling agents, biocides, metal deactivators, flameretardants, antifogging agents and compatibilizers are described in“HANDBUCH DER KUNSTSTOFFADDITIVE”, R. Gächter/H. Müller, Carl HanserVerlag, 3rd Ed., 1989, and 4th Ed., 2001, and in “HANDBOOK OF POLYVINYLCHLORIDE FORMULATING” E. J. Wickson, J. Wiley & Sons, 1993, and also in“PLASTICS ADDITIVES” G. Pritchard, Chapman & Hall, London, 1st Ed.,1998. Impact modifiers are also described in detail in “IMPACT MODIFIERSFOR PVC”, J. T. Lutz/D. L. Dunkelberger, John Wiley & Sons, 1992.

Further stabilizers may be 2-phenylindole, 2-pyrrolocarboxylicacid/esters, 2,4-diphenylpyrrole and2-alkyl-4-phenylpyrrolo-3-carboxylic esters, and also3-amino-4-alkyl/phenylpyrrolo-3-carboxylic esters (on this subject, seeEP 1,299,466 A1).

Preference is also given to stabilizer systems which additionallycomprise a substituted indole or a urea or an aniline derivative.Examples of suitable compounds are 2-phenyllaurylindole andN,N′-diphenylthiourea, and also phenylurea. Further examples aredescribed in PS-DE 101,07,329 A1. On this subject, see also PS-EP0,768,336 A1, EP 0,174,412, EP 0,967,245 A1, EP 0,967,209 A1, EP0,967,208 A1, EP 0,962,491 A1, EP 1,044,968 A1, WO 02/072 684 and WO02/048 249.

A particular preference lies in the combination of the (A)/(B-1), (B-2),(C-1), (C-2)+SCV or AS blends (especially (D), (E) and (F)) withphosphite esters, the additional phosphite being distearylpentaerythrityl diphosphite, triphenyl phosphite, tris(nonyl)phenylphosphite, phenyl didecyl phosphite, poly(dipropylene glycol) phenylphosphite, tetraphenyl dipropylene glycol diphosphite,tetraisodecyl(dipropylene glycol) diphosphite, tris(dipropylene glycol)phosphite, decyl diphenyl phosphite, trioctyl phosphite, trilaurylphosphite or (nonylphenyl)_(1.5)-C₁₂/C₁₃-alkyl)_(1.5)-phosphite.

In the inventive compositions, the compounds of the general formulae(B-1/B-2) or (C-1/C-2)+SCV or AS, to achieve stabilization in thechlorinated polymer, should be used appropriately in an amount of 0.01to 10, preferably of 0.05 to 5, based on 100 parts by weight of polymer.The inner complexes (A) will be employed in an amount of, for example,0.001 to 10 parts, appropriately 0.01 to 5 parts, more preferably 0.01to 3 parts by weight, based on 100 parts by weight of polymer.Preference is given to compositions in which the ratio of the compoundof the general formulae (B) and (C) to the inner complexes (A), based onthe weight, is in the range of 4:8:1 to 6:30:1.

Preference is given to compositions comprising 0.01 to 10 parts byweight of sterically hindered amine and/or NOR-HALS compound (G1-G5)and/or UV absorber and/or titanium dioxide.

Preferred compositions contain, based on 100 parts by weight ofchlorinated polymer, 0.01-10 parts by weight of compound (B) and 0.01-10parts by weight of compound (C) for 0.001-1 part by weight of the innercomplexes (A).

Examples of the chlorinated polymers to be stabilized are polymers ofvinyl chloride, of vinylidene chloride, vinyl resins containing vinylchloride units in their structure, such as copolymers of vinyl chlorideand vinyl esters of aliphatic acids, especially vinyl acetate,copolymers of vinyl chloride with esters of acrylic acid and methacrylicacid and with acrylonitrile, copolymers of vinyl chloride with dienecompounds and unsaturated dicarboxylic acids or their anhydrides, suchas copolymers of vinyl chloride with diethyl maleate, diethyl fumarateor maleic anhydride, post-chlorinated polymers and copolymers of vinylchloride, copolymers of vinyl chloride and of vinylidene chloride withunsaturated aldehydes, ketones and others, such as acrolein,crotonaldehyde, vinyl methyl ketone, vinyl methyl ether, vinyl isobutylether and the like; polymers of vinylidene chloride and copolymersthereof with vinyl chloride and other polymerizable compounds; polymersof vinyl chloroacetate and of dichlorodivinyl ether; chlorinatedpolymers of vinyl acetate, chlorinated polymeric esters of acrylic acidand of alpha-substituted acrylic acid; polymers of chlorinated styrenes,for example dichlorostyrene; chlorine rubbers; chlorinated polymers ofethylene; polymers and post-chlorinated polymers of chlorobutadiene andthe copolymers thereof with vinyl chloride, chlorinated natural andsynthetic rubbers, and mixtures of the polymers mentioned with oneanother and with other polymerizable compounds. In the context of thisinvention, PVC is also understood to mean copolymers of vinyl chloridewith polymerizable compounds such as acrylonitrile, vinyl acetate orABS, and the polymers may be suspension polymers, bulk polymers oremulsion polymers.

Preference is given to a PVC homopolymer, also in combination withpolyacrylates or polymethacrylates.

Also useful are graft polymers of PVC with EVA, ABS and MBS, as aregraft polymers of PVC with PMMA. Preferred substrates are also mixturesof the aforementioned homo- and copolymers, especially vinyl chloridehomopolymers, with other thermoplastic or/and elastomeric polymers,especially blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA,EPDM and polylactones, especially from the group of ABS, NBR, NAR, SANand EVA. The abbreviations used for the copolymers are familiar to thoseskilled in the art and mean the following: ABSacrylonitrile-butadiene-styrene; SAN styrene-acrylonitrile; NBRacrylonitrile-butadiene; NAR acrylonitrile-acrylate; EVA ethylene-vinylacetate. Especially useful are also styrene-acrylonitrile copolymersbased on acrylate (ASA). Preferred components in this connection arepolymer compositions which contain, as components (i) and (ii), amixture of 25-75% by weight of PVC and 75-25% by weight of thecopolymers mentioned. Of particular significance as components arecompositions composed of (i) 100 parts by weight of PVC and (ii) 0-300parts by weight of ABS and/or SAN-modified ABS and 0-80 parts by weightof the copolymers NBR, NAR and/or EVA, but especially EVA.

In addition, useful substances for stabilization in the context of thisinvention are also especially recyclates of chlorinated polymers, whichare the polymers described in detail above which have experienced damagethrough processing, use or storage. Particular preference is given toPVC recyclate. A further use of the inventive stabilizer combinations isbased on imparting antistatic properties to the finished articlecomposed of rigid or flexible PVC. In this way, it is possible to reducethe use of expensive antistats. For this application, preference isgiven to flexible PVC or semirigid PVC.

The present invention further provides a composition comprising flexiblePVC and a stabilizer system which comprises 1,4-cyclohexanedimethanoldiglycidyl ether.

The invention further provides goods for use (useful articles) whichcomprise PVC and inventive systems.

Preference is also given to the use of items for use which are notablefor a particular fine foam structure. This is the case for rigid PVC,flexible PVC and semirigid PVC. This aspect is particularly important inthe case of wallpaper and floors composed of flexible PVC. Normally,heavy metal compounds such as Zn or Sn stabilizers are required askickers to achieve a fine foam. It has been found that, surprisingly,TEA inner complexes exert a kicker action on isatoic anhydride orN-methylisatoic anhydride, which ensures the achievement of a fine foamstructure.

Nor was it foreseeable that the electrical resistance properties of anitem for use which comprises TEA inner complexes as one component areimproved significantly, which is found to be favourable especially incable and insulator production and in applications in the semiconductorsector.

In addition, these items (mainly cables) are severed better when storedin water, since the formulations do not contain any zinc soaps and thusno zinc chloride is formed in the course of processing, which, aftermigration to the plastic surface, worsens the electrical values.

Moreover, in the case of zinc-sensitive applications, mainly in theflexible PVC sector (for example films, roof sheeting) which absolutelyneed biocidal modification, it is possible to add zinc-containingfungicides, which greatly restricts the use of calcium-zinc stabilizers.

The useable compounds and the chlorinated polymers are known in generalterms to those skilled in the art and are described in detail in“HANDBUCH DER KUNSTOFFADDITIVE”, R. Gächter/H. Müller, Carl HanserVerlag, 3rd Ed., 1989 and 4th Ed. 2001, in PS-DE 197,41,778 A1 and EP0,967,245 A1, to which reference is hereby made explicitly.

The inventive stabilization is suitable especially for chlorinatedpolymer compositions which are unplasticized or plasticizer-free or areessentially plasticizer-free compositions, and also for plasticizedcompositions. Particular preference is given to applications in rigidPVC or semirigid PVC.

The inventive compositions are suitable especially, in the form offormulations for rigid PVC, for hollow bodies (bottles), packaging films(thermoforming films), blown films, “Crash Pad” films (automobiles),tubes, foams, heavy profiles (window frames), light wall profiles,building profiles, films, blister packaging (including that produced bythe Luvitherm process), profiles, sidings, fittings, office films,margarine tubs, packaging for chocolates and apparatus casings,insulators, computer casings and constituents of household appliances,and also for electronic applications, especially in the semiconductorsector. These are very particularly suitable for producing windowprofiles with high whiteness and surface shine. Preferred othercompositions in the form of formulations for semirigid and flexible PVCare suitable for wire sheathing, cable insulation, decorative films,roof films, foams, agrochemical films, pipes, sealing profiles, floors,wallpaper, motor vehicle parts, flexible films, injection mouldings(blow-moulding), office films and films for air-inflated marquees.Examples for the use of the inventive compositions as plastisols aretoys (rotomoulding), synthetic leather, floors, textile coatings,wallpaper, coil coatings and underbody protection for motor vehicles.Examples of sintered PVC applications of the inventive compositions areslush, slush mould and coil coatings, and also in E-PVC for filmsproduced by the Luvitherm process. For further details on this subjectsee “KUNSTSTOFFHANDBUCH PVC”, volume 2/2, W. Becker/H. Braun, 2nd Ed.1985, Carl Hanser Verlag, p. 1236-1277.

Components (A) and (B-1)/(B-2) and/or (C-1)/(C-2) may be premixedtogether with other stabilizers or additives or PVC substrates, in whichcase further stabilizers present may preferably be alkaline earth metalhydroxides, zeolites, hydrotalcites, glycidyl compounds or melamine.Very particular preference is given here to so-called hot mixers whichwork within a temperature range of 80° C. up to 120° C. In this case,optimal homogenization is achieved. In the presence of PVC powder,stabilizers and further additives diffuse into the PVC grain. Onevariant consists in performing the mixing operation in a lubricant meltwhich may comprise calcium stearate or magnesium laurate or magnesiumstearate or (hydroxy) stearic acid, in the presence of a calciumhydroxide or magnesium hydroxide, of a basic magnesium, calcium oraluminium salt, or of overbased compounds of magnesium and calcium, orof a polyol or of a zeolite, preference being given to maltitol,lactitol, palatinitol or zeolite A, calcium hydroxide, a basic calciumor magnesium salt or an overbased compound of magnesium or calcium.

Particular preference is given to the embodiment in which components(B-1)/(B-2) or/and (C-1)/(C-2)+SCV (especially (D), (E) and calciumhydroxide or melamine) are initially charged in this melt, and component(A) is metered in, it being possible for components (F) and (G) to bepresent in the premixture.

Appropriately, the stabilizers can be incorporated in another variant bythe following methods: as an emulsion or dispersion (one possibility is,for example, the form of a pasty mixture, one advantage of the inventivesystem in this administration form is the stability of the paste); as adry mixture during the mixing of additional components or polymermixtures; by direct addition to the processing apparatus (e.g. calender,mixer, kneader, extruder and the like) or as solution or melt, or asflakes or pellets in dust-free form as a one-pack.

Particular preference is given to premixtures of component (A) with(B-1)/(B-2) or (C-1)/(C-2) with SCV (especially (D), (E) and calciumhydroxide or melamine), and optionally (F) or/and (G), in compactedform, produced in granulating apparatus, to obtain a non-dusting,non-tacky, free-flowing granule which can be digested very readily whenblended with, for example, PVC and during the processing operation. Itis highly advantageous, during the finishing (compaction or sprayingoperation) to add binders, which preferably consist of cellulose ethersor esters (mainly hydroxyethyl-, hydroxypropyl- andhydroxypropylmethylcellulose or carboxymethylcellulose). Alternatively,it is also possible to add polyvinyl alcohol or polyvinylpyrrolidone.

In addition to wet granulation, preference is given to dry granulation,which, in the presence of fatty acid salts of magnesium or calcium ormetal-free lubricants based on esters or hydrocarbons, leads to anon-dusting free-flowing cylinder granule. In the presence oflubricants, preferably ester waxes, flakes, slugs or pellets areobtained in the melt granulation and are very easily dispersible in PVC.

The polymer stabilized in accordance with the invention can be preparedin a manner known per se, for which the inventive stabilizer mixture andany further additives are mixed with the polymer using apparatus knownper se, such as the processing apparatus mentioned above. At the sametime, the stabilizers can be added individually or in a mixture or elsein the form of so-called masterbatches.

The polymer stabilized in accordance with the present invention can bebrought into the desired form by known methods. Such methods are, forexample, grinding, calendering, extrusion, injection moulding orspinning, and also extrusion blow-moulding. The stabilized polymer mayalso be processed to foams. The invention thus also provides a processfor stabilizing chlorinated polymers by adding the inventive stabilizermixture to a chlorinated polymer, and also articles which comprise PVCwhich is stabilized by the inventive stabilizer mixtures.

The invention further provides a process for stabilizing chlorinatedpolymers by adding an inventive stabilizer system to a chlorinatedpolymer, especially to flexible PVC or PVC paste. The flexible PVC maybe suitable for the manufacture of floors, motor vehicle parts,wallpaper, flexible films, pipes, injection mouldings or preferably forwire sheathing (cables). Alternatively, the chlorinated polymer may alsobe rigid PVC. The chlorinated polymer may also serve for the productionof films (including Luvitherm), PVC pipes or profiles, preferably windowprofiles.

The inventive inner complexes may be prepared in methanol, ethanol,propanol, triethanolamine or water, and the solvent and any water ofreaction are removed by distillation. The distillation residue cansubsequently be digested in a nonpolar solvent and be removed byfiltration. Alternatively, the synthesis can be effected in an alcoholand the reaction product can then be precipitated by adding a nonpolarsolvent.

EXAMPLES

These illustrate the invention in detail. Parts data are based—as alsoin the rest of the description—unless stated otherwise, on the weight.

1. Synthesis Examples 1.1 Triethanolamineperchlorato(triflato) InnerComplexes 1.1.1 TEA-perchloratosodium (TEAP)-[(TEA)Na(OClO₃)]

In a 1 l pear-shaped flask, 35.2 g of sodium perchlorate monohydrate(NaP*H₂O, 0.25 mol) and 37.3 g of triethanolamine (TEA, 0.25 mol) aredissolved in 100 ml of methanol. The reaction mixture is concentrated todryness on a rotary evaporator at 72° C. (under reduced pressure towardsthe end), which also removes the water of hydration. This affords theanhydrous compound in crystalline form. The resulting product is driedin vacuo. Yield 67 g (quantitative), m.p.: 131° C. (sharp).

It is also possible to use aqueous NaP solutions, in which casestoichiometric amounts of TEA, dissolved in methanol, ethanol,isopropanol, THF, acetone or water, are added. Another alternativeconsists in using NaP(H₂O) suspensions in organic solvents, such asacetone, THF, glycol ethers (dimethoxyethane), isopropanol, dioxane,DMF, DMA, acetonitrile, etc.

The workup can likewise be modified by precipitating the TEA innercomplexes from the above solutions by addition of relatively non-polarsolvents such as acetic esters, hydrocarbons (aromatic or aliphatic),chlorinated hydrocarbons, ethers (MTBE), in the form of cluster-shapedcrystals (see FIG. 1). These modifications may also be applied to theexamples which follow.

1.1.2 Bis-TEA-perchloratocalcium (TECAP)-[(TEA)₂Ca(OClO₃)₂]

In a 1 l pear-shaped flask, 38.9 g of calcium perchlorate tetrahydrate(0.125 mol) and 37.3 g of triethanolamine (TEA, 0.25 mol) are dissolvedin 100 ml of methanol. The reaction mixture is concentrated to drynesson a rotary evaporator at 72° C. (under reduced pressure towards theend), which also removes the water of hydration. This affords theanhydrous crystalline product. The resulting compound is dried in vacuo.Yield 67 g (quantitative), m.p.: >280-285° C. (decomposition—darkeningof colour).

1.1.3 TEA-triflatosodium (TEAT)-[(TEA)Na(OSO₂CF₃)]

In a 1 l pear-shaped flask, 43.0 g of sodium triflate (0.25 mol) and37.3 g of triethanolamine (TEA, 0.25 mol) are dissolved in 100 ml ofmethanol. The reaction mixture is concentrated to dryness on a rotaryevaporator at 72° C. (under reduced pressure towards the end), whichalso removes the water of hydration. This affords the anhydrouscrystalline product. The resulting compound is dried in vacuo. Yield 80g (quantitative), m.p.: 97° C. (indistinct).

1.1.4 Bis-TEA-perchloratozinc (TEZIP)-[(TEA)₂Zn(OClO₃)₂]

In a 1 l pear-shaped flask, 4.7 g of zinc perchlorate hexahydrate (12.5mmol) and 3.7 g of triethanolamine (TEA, 25 mmol) are dissolved in 20 mlof methanol. The reaction mixture is concentrated to dryness on a rotaryevaporator at 72° C. (under reduced pressure towards the end), whichalso removes the water of hydration. This affords the anhydrouscrystalline product. The resulting compound is dried in vacuo. Yield 7.0g (quantitative), m.p.: glass-like sintering from 80° C.; 230-250° C.yellow to brown, liquid.

1.2. Dihydropyridine Compounds (DHPs)²⁾

1.2.1 Dimethyl 4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylate(mono-DHP)

In a 1 l round-bottomed flask, 73.5 g of methyl β-aminocrotonate, (MAC;0.64 mol) and 30 g of formalin (37%) (1.1 mol) are dissolved in 500 mlof isopropanol, and stirred at 60° C. for 1 h. Subsequently, the mixtureis heated at reflux for 6 h, in the course of which a yellow solidforms. The suspension is subsequently stirred into water and theprecipitate is filtered off. The precipitate is washed with water, thenwith acetone, and dried in vacuo.

Yield: 57.4 g (corresponds to 80% of theory), m.p.: 224-225° C. ²⁾ Basedon PS-EP286887

1.2.2 Bis[1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylicacid]1,4-butanediol Diester (bis-DHP)

In a 1 l round-bottomed flask, 64.1 g of 1,4-butanediolbis-3-aminocrotonate (BAC; 0.25 mol) are dissolved with 57.6 g of methylβ-aminocrotonate, (MAC; 0.5 mol) and 75 g of formalin (37%) in 500 ml ofisopropanol, and stirred at 60° C. for 1 h. Subsequently, the mixture isheated at reflux for 6 h, in the course of which a yellow solid forms.The suspension is subsequently stirred into water and the precipitate isfiltered off. The precipitate is washed with water, then with acetone,and dried in vacuo.

Yield: 81 g (corresponds to 73% of theory), m.p.: 192-194° C.

1.2.3 Bis[1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylicacid]thiodiethylene Glycol Diester (bis-thio-DHP)

In a 1 l round-bottomed flask, 72.1 g of thiodiglycolbis(aminocrotonate) (TAC; 0.25 mol) are dissolved with 57.6 g of methylβ-aminocrotonate (MAC; 0.5 mol) and 75 g of formalin (37%) in 500 ml ofisopropanol, and stirred at 60° C. for 1 h. Subsequently, the mixture isheated at reflux for 6 h, in the course of which a yellow solid forms.The suspension is subsequently stirred into water and the precipitate isfiltered off. The precipitate is washed with water, then with acetone,and dried in vacuo.

Yield: 64.5 g (corresponds to 56% of theory), m.p.: 148-152° C.

1.2.4 Poly[1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylicacid]1,4-butanediol Ester (poly-DHP)

In a 1 l round-bottomed flask, 76.4 g of 1,4-butanediolbis(3-aminocrotonate) (BAC; 0.298 mol) are dissolved with 4.9 g ofmethyl β-aminocrotonate (MAC; 0.0426 mol) and 30 g of formalin (37%) in500 ml of isopropanol, and stirred at 60° C. for 1 h. Subsequently, themixture is heated at reflux for 6 h, in the course of which a yellowsolid forms. The suspension is subsequently stirred into water and theprecipitate is filtered off. The precipitate is washed with water, thenwith acetone, and dried in vacuo.

Yield: 63.9 g (corresponds to 80% of theory), m.p.: 218-220° C.

1.2.5 Poly[1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylic AcidThiodiethylene Glycol Ester](poly-thio-DHP)

In a 1 l round-bottomed flask, 86.5 g of thiodiglycolbis(aminocrotonate) (TAC; 0.30 mol) are dissolved with 4.9 g of methylβ-aminocrotonate (MAC; 0.0426 mol) and 30 g of formalin (37%) in 500 mlof isopropanol, and stirred at 60° C. for 1 h. Subsequently, the mixtureis heated at reflux for 6 h, in the course of which a yellow solidforms. The suspension is subsequently stirred into water and theprecipitate is filtered off. The precipitate is washed with water, thenwith acetone, and dried in vacuo.

Yield: 76.3 g (corresponds to 85% of theory), m.p.: 168-170° C.

2. Application Examples 2.1 Studies of Dehydrochlorination (DHC) 2.1.1Preparation of the Powder Samples

A 1 l pear-shaped flask is initially charged with 5 or 10 g (correspondsto 100 phr) of PVC^(a)), and the additives according to the tableexamples are added. The mixtures consist of 1.6 phr of HCl scavenger(SCV), 0.4 phr of initial colour improver (ICI) and the appropriateamounts of TEAP booster (0.16 phr). Subsequently, 50 ml of methanol areadded and this slurry is concentrated to dryness on a rotary evaporatorat 72° C./reduced pressure. The resulting powder mixtures arehomogenized in an Achat mortar. (The method is preferably for one or twoliquid additives. When all additives are solid, sole homogenization canbe effected in the Achat mortar, and the process of MeOH slurrying canbe dispensed with.)

2.1.2 Performance of the Dehydrochlorination Measurements

The DHC is a measure of the HCl elimination of PVC, which takes place onthermal stress. The eliminated hydrochloric acid is flushed withnitrogen gas into a reservoir comprising dist. water, and the rise inconductivity in microsiemens per centimetre (μS/cm) is measured there.The characteristics used are the accompanying minute values (min). Thelonger the time interval to achieve a particular conductivity, the morethermally stable is the PVC sample.

Instrument type: PVC thermomat 763 (from Metrohm)

The measurements were effected to DN 53381 Part 1, Method B:Conductivity measurement.

Parameters: Initial sample weight: 500 ± 5 mg Temperature: 180° C. Flow:7 l/h (nitrogen 5.0) Absorption vol.: 60 ml (demineralized water)Evaluation: t₁₀, t₅₀ and t₂₀₀ (conductivity of 10, 50 and 200 μS/cm -data in minute values)

Measurement: after the powder samples have been weighed into thereaction vessels, the measurement vessels are filled with demineralizedwater and equipped with conductivity electrodes. On attainment of themeasurement temperature (180° C.), the closed reaction vessels aretransferred to the heating block and coupled to the measurement vesselsvia the appropriate pipe connections, and the measurement is started.The stability criteria used are the t₁₀, t₅₀ and t₂₀₀ values.

2.1.3 Examples 2.1.3.1 Effect of (A) as a Singular PVC Stabilizer (Tab.1)

Experiment 1: 100 phr of PVC³⁾ without stabilizer (booster)

Experiment 2: 100 phr of PVC³⁾+booster ³⁾ Vinnolit S 3160, K value 60

TABLE 1 Experiment t₁₀ t₅₀ t₂₀₀ TEAP⁴⁾ No. [min] [min] [min] [phr] 1 619 44 — 2 30 59 154 0.16 ⁴⁾Triethanolamineperchloratosodium (SynthesisExample 1.1.1) ⁵⁾Calcium hydroxide (uncoated) ⁶⁾Calcium hydroxide(coated with 7% Edenor L2SMGS - Cognis)

It is evident that the inventive formulation (Experiment 2), compared tounstabilized PVC, has a drastic rise in the thermal stabilization(t₁₀=400%, t₅₀=210% and t₂₀₀=250%).

2.1.3.2 Effect of (A) as a PVC Stabilizer (in the Presence of HClScavenger SCV) 2.1.3.2.1 Inorganic (Mineral) Compounds as SCV (Tab. 2)

TABLE 2 Experiment t₁₀ t₅₀ t₂₀₀ TEAP No. SCV [min] [min] [min] [phr]  3CaH (u)⁵⁾ 130 201 398 0.16  4 CaH (c)⁶⁾ 168 252 444 0.16  5 CaH (u)⁵⁾ 3758 124 —  6 CaH (c)⁶⁾ 34 46 75 —  7 Hytal⁷⁾ 89 125 235 0.16  8 Hytal⁷⁾43 56 88 —  9 Sorbacid 939⁸⁾ 76 116 238 0.16 10 Sorbacid 911⁸⁾ 114 146251 0.16 11 Sorbacid 939⁸⁾ 29 43 88 — 12 Sorbacid 911⁸⁾ 55 66 94 — 13Pural MG63HT⁹⁾ 128 170 331 0.16 14 Pural MG63HT⁹⁾ 55 65 93 —  14a DASC265^(9a)) 100 166 343 0.16  14b DASC 265^(9a)) 34 52 100 — 15 NaZA¹⁰⁾ 80112 228 0.16 16 NaZA¹⁰⁾ 26 38 73 — 17 MgH¹¹⁾ 43 113 163 0.16 18 MgH¹¹⁾13 11 46 — 19 CaAcac¹²⁾ 111 170 326 0.16 20 CaAcac¹²⁾ 50 69 118 — 21MgAcac¹³⁾ 92 112 166 0.16 22 MgAcac¹³⁾ 79 87 115 — ⁵⁾Calcium hydroxide(uncoated) ⁶⁾Calcium hydroxide (coated with 7% Edenor L2SMGS - Cognis)⁷⁾Hydrotalcite (ALDRICH) ⁸⁾Hydrotalcite (from Südchemie) ⁹⁾Hydrotalcite(from Sasol) ^(9a))Dihydroxyaluminum sodium carbonate, type A 265 (fromB K Giolini) ¹⁰⁾Sodium zeolite A (molecular sieve. 4A powder <5 microns,activated – ALDRICH) ¹¹⁾Magnesium Hydroxide (FLUKA) ¹²⁾Calciumacetylacotonate (from MCC) ¹³⁾Magnesium Acetylacotonate (ALDRICH)¹⁵⁾Sodium perchlorate monohydrate (MERCK)

The results show that the effect of uncoated and coated calciumhydroxide by virtue of addition of catalytic amounts of TEAP is improvedhighly efficiently with regard to initial, intermediate and finalstability.

It has been found that the performance of commercially availablemagnesium aluminium hydrocarbonates (hydrotalcites, LDHs, anionic clays)can be improved significantly by addition of TEAP.

The findings show that the thermal stabilizer effect of commerciallyavailable sodium zeolite A is improved significantly when TEAP is added.

Here too, addition of TEAP can clearly achieve a significant rise in thethermal stability.

2.1.3.2.1.1 Comparison with Prior Art (PA¹⁴)—Tab. 3

TABLE 3 Experiment t₁₀ t₅₀ t₂₀₀ NaP ¹⁵⁾ No. SCV [min] [min] [min] [phr]23 CaH(u) ⁵⁾ 73 126 267 0.08 24 Hytal ⁷⁾ 82 109 182 0.08 25 NaZA ¹⁰⁾ 4875 156 0.08 ¹⁵⁾ Sodium perchlorate monohydrate (MERCK)

A comparison of Experiment 23 (CaH with sodium perchlorate) withExperiment 3 (CaH with TEAP, based on equal numbers of moles of NaP)shows that, when TEAP is used, a 78% rise is recorded in the t₁₀ value,a 60% rise in the t₅₀ value and a 49% rise in the t₂₀₀ ¹⁴⁾ General priorart value. Moreover, the comparison of Experiments 24 and 25 (Hytal+NaPand NaZA+NaP) with Experiments 7 and 15 (Hytal+TEAP and NaZA+TEAP) showsa significant improvement in the thermal stability when TEAP is used asa booster.

2.1.3.2.1.2 PA-1¹⁶⁾

PS-DE 10124734A1 (PA-1) states that aqueous sodium perchlorate solutionsshould be applied to calcium oxide in the presence of calcium hydroxide,the water of the solution being bound according to:

CaO+H₂O→Ca(OH)₂

this results in a solid which comprises, as components, NaClO₄ (orNaClO₄*H₂O) and Ca(OH)₂. ¹⁶⁾ Specific prior art 1

These substances are used as PVC thermal (co)stabilizers. In a series,the products obtained by given processes were compared with CaH/TEAP(1.6/0.16 phr) in equal amounts, with equal CaH amounts, and with equal(molar) amounts of ClO₄, to obtain the following results (Tab. 4).

TABLE 4 Exper- iment Stabilizer system Σ Stab. t₁₀ t₅₀ t₂₀₀ No.Substance/(amount) [phr] [phr] [min] [min] [min] Remark 26 TEAP(reference) 1.760 146 220 403 Inventive, yellow CaH (1.6) colour TEAP(0.16) ¹⁷⁾ 27 VP-1 ¹⁸⁾ (equal CaH) 1.760 85 143 279 According to CaH(1.6) PA-1, NaP (0.16) orange colour 28 VP-1 ¹⁸⁾ (equal NaP) 0.72 39 70164 According to CaH (0.648) PA-1, NaP (0.072) orange colour 29 CaH/NaP(external) 1.672 91 166 344 Not patented, CaH (1.6) yellow colour NaP(0.072) 30 VP-2 ¹⁸⁾ (equal CaH/NaP) 1.672 85 149 300 According to CaH(1.6) PA-1, NaP (0.072) orange colour ¹⁷⁾ 0.16 phr of TEAP correspondsto 0.072 phr of NaClO₄ × H₂O (equal ClO₄) ¹⁸⁾ VP-1,2 = Experimentalproducts according to PA PS DE 10124734A1 (Example 3)

The patented (PA-1) DHC values are averaged over several experiments.The comparison of Experiment 26 with Experiment 27 shows, with the sametotal amount of stabilizer (Σ stab.) (1.76 phr) and equal CaH (1.6 phr),a rise in the t_(10, 50, 200) values by 72%, 54% and 44%. An additionalfactor is that the NaP content in Experiment 27 is increased by a factorof 2, which greatly increases the proportional cost factor. A comparisonof the patented PA-1 internal mixtures with unpatented external mixtures(Experiment 27, 29) shows a poorer performance for the former(patented). A comparison shows that, with equal CaH and NaP (Experiment26 compared to patented Experiment 30), there is an improvement ineffect in relation to the t_(10, 50, 200) values by 72%, 48% and 34%.Moreover, the PVC powder samples, after the end of the experiment, inthe patented (PA-1) experiments (27, 28, 29), show a significantlydarker colour, even though the thermal stress (180° C.) of the PAsamples at 279, 164 and 300 min was significantly lower than theinventive Experiment 26, which was thermally stressed over a period of403. The unpatented Experiment 29 likewise has a significantly lighteryellow colour after longer thermal stress.

2.1.3.2.1.3 PA-2¹⁹⁾

PS-DE 10160662A1 and DE 10214152A1 (PA-2) claim onium (ammonium)perchlorate salts as heat (co) stabilizers. In one series, the closestcompounds (PA-2) were compared with inventive CaH/TEAP systems in equaluse amounts (CaH+booster=1.6+0.16 phr) (Tab. 5 and 6). ¹⁹⁾ Specificprior art 2

TABLE 5 ClO₄ Synonym/ content M.W. m.p. Substance Name abbreviation[%_(calc.)] [g/mol] [° C.]

Triethanolamine- perchloratosodium TEAP 36.6 271.7  132

Monohydroxyethyl- diethylammonium perchlorate MEHAP 45.7 217.7 <RT

Trihydroxyethyl- ammonium perchlorate TREHAP 39.9 249.7  40

Tetraethylammonium perchlorate TEHAP 43.3 229.8 >300

TABLE 6 Experiment Substance t₁₀ t₅₀ t₂₀₀ No. (Tab. 5) [min] [min] [min]Remark 31 TEAP 152 228 420 No amine perchlorate (reference) Yellowcolour 32 MEHAP 108 167 327 Amine perchlorate Yellow-orange colour 33TREHAP 64 106 206 Amine perchlorate Orange-brown colour 34 TEHAP 38 71152 No amine perchlorate Light brown colour

The quality factors (improvement in performance) of the inventive system(Experiment 31) compared to Experiment 32 are 41%, 37% and 28%; comparedto Experiment 33, 38%, 115% and 104%; and compared to Experiment 34 (allPA-2), 300%, 221% and 176%, with regard to the t_(10, 50, 200) values.This demonstrates clear superiority over PA-2. Moreover, the samplesaccording to PA-2, after the thermal stress, are more strongly colouredthan the inventive samples, even though the thermal stress times of 327,206 and 152 min are significantly lower than that of 420 min forExperiment 31.

What is conspicuous is the moderate finding for 33 (TREHAP), which, in aformal sense, is similar to TEAP (exchange of H for Na). The improvementin performance for this compound is reported above. In terms ofactivity, Experiment 34 (TEHAP) declines even further, which is probablybecause it is not an amine perchlorate but rather a (true) (amm)oniumperchlorate, and the onium salt structure exerts a contrary(destabilizing) effect.

The amine perchlorates 31 and 32 are, as NH perchlorates, critical intheir handling, since they are shock-sensitive and explosive. Equally,perchloric acid is absolutely necessary for their preparation, which hasspecific labelling requirements as a risk substance with the symbol forirritant and the R statement 5-8-35.

2.1.3.2.2 Organic Compounds as SCV (Tab. 7 and 8)

TABLE 7 Experiment SCV t₁₀ t₅₀ t₂₀₀ TEAP No. Cyanamide [min] [min] [min][phr] 35 Didi-f²⁰⁾ 59 64 75 — 36 Didi-n²¹⁾ 56 61 70 — 37 Didi-f²⁰⁾ 82 99132 0.16 38 Mel-n²²⁾ 61 65 79 — 39 Mel-f²³⁾ 49 53 65 — 40 Mel-f²³⁾ 145175 265 0.16 41 ACEGA²⁴⁾ 31 35 44 — 42 ACEGA²⁴⁾ 113 146 240 0.16²⁰⁾Dyhard 100SH, cyanoguanidine (dicyandiamide), fine particles (fromDegussa) ²¹⁾Cyanoguanidine (dicyandiamide), normal particles (fromDegussa) ²²⁾Melamine - normal particles (ALDRICH) ²³⁾Melamine 003fine-particle product (from DSM) ²⁴⁾Acetoguanamine (ALDRICH)

It is evident that TEAP addition to cyanoguanidine gives rise to asignificant improvement in the thermal stability (t₁₀=39%, t₅₀=55%,t₂₀₀=76%).

It is found that the inventive combination of aminotriazine/TEAP(Experiment 40), compared to the non-inventive formulation (Experiment39), gives rise to a relevant improvement stimulus in the thermalstabilization (t₁₀=196%, t₅₀=230%, t₂₀₀=308%). In addition, it isevident that the combination of acetoguanamine/TEAP (Experiment 42),compared to Experiment 41 (without TEAP), is significantly morethermally stable (t₁₀=265%, t₅₀=317%, t₂₀₀=445%).

TABLE 8 Experiment SCV t₁₀ t₅₀ t₂₀₀ NaP TEAP No. Epoxide [min] [min][min] [phr] [phr] 43 BADGE ²⁵⁾ 18 34 74 — — 44 BADGE ²⁵⁾ 42 84 234 —0.16 45 BADGE ²⁵⁾ 19 40 110 0.08 — 46 BFDGE ²⁶⁾ 16 30 68 — — 47 BFDGE²⁶⁾ 39 77 205 — 0.16 48 BFDGE ²⁶⁾ 22 44 115 0.08 — 49 Epikote 828 ²⁷⁾ 1428 67 — — 50 Epikote 828 ²⁷⁾ 68 124 276 — 0.16 51 Epikote 828 ²⁷⁾ 28 58154 0.08 — 52 Epikote 1002 ²⁸⁾ 14 28 72 — — 53 Epikote 1002 ²⁸⁾ 36 62150 — 0.16 54 Epikote 1002 ²⁸⁾ 25 74 117 0.08 — 55 Hexdge ²⁹⁾ 35 52 92 —— 56 Hexdge ²⁹⁾ 122 150 270 — 0.16 57 Hexdge ²⁹⁾ 46 66 133 0.08 — 57ac-Hexdge ^(29a)) 128 153 246 — 0.16 57b c-Hexdge ^(29a)) 25 43 101 0.08— 58 Glydi ³⁰⁾ 40 57 89 — — 59 Glydi ³⁰⁾ 103 130 201 — 0.16 60 Glydi ³⁰⁾37 61 127 0.08 — 61 Glytri ³¹⁾ 25 44 82 — — 62 Glytri ³¹⁾ 70 100 186 —0.16 63 Glytri ³¹⁾ 37 60 128 0.08 — 64 TEPC ³²⁾ 64 100 156 — — 65 TEPC³²⁾ 185 240 374 — 0.16 66 TEPC ³²⁾ 119 173 260 0.08 — 67 LankL ³³⁾ [3.2phr] 17 37 93 — — 68 LankL ³³⁾ [3.2 phr] 34 56 146 — 0.16 69 LankL ³³⁾[3.2 phr] 24 44 116 0.08 — 70 Lank07 ³⁴⁾ [3.2 phr] 16 31 71 — — 71Lank07 ³⁴⁾ [3.2 phr] 31 56 151 — 0.16 72 Lank07 ³⁴⁾ [3.2 phr] 23 46 1270.08 — 73 Card ³⁵⁾ [3.2 phr] 25 39 83 — — 74 Card ³⁵⁾ [3.2 phr] 41 72197 — 0.16 75 Card ³⁵⁾ [3.2 phr] 38 68 179 0.08 — ²⁵⁾ Bisphenol Adiglycidyl ether (ALDRICH) ²⁶⁾ Bisphenol F diglycidyl ether (ALDRICH)²⁷⁾ Bisphenol A diglycidyl ether - liquid (from Resolution) ²⁸⁾Bisphenol A diglycidyl ether - solid (from Resolution) ²⁹⁾ Hexanediol1,6-diglycidyl ether (Grilonit RV 1812, from EMS - Primid) ^(29a))1,4-Cyclohexanedimethanol diglycidyl ether (POLYPOX R11, from UPPC-AG)³⁰⁾ Glycerol diglycidyl ether (ALDRICH) ³¹⁾ Glycerol triglycidyl ether(Glycidether 100, ROTH) ³²⁾ Tris(2,3-epoxypropyl) isocyanurate(ALDRICH) - Triglycidyl isocyanurate ³³⁾ Lankroflex L (from AkzoNobel) - epoxidized linseed oil ³⁴⁾ Lankroflex 2307 (from Akzo Nobel) -ESBO ³⁵⁾ Cardura E10P (from Resolution) - Glycidyl neodecanoate

It is found that all epoxy compounds, when TEAP is added, bring asignificant improvement in the t₁₀ values of 144% (Experiment 46 vs. 47)to 189% (Experiment 64 vs. 65), in the t₅₀ values of 104% (Experiment 55vs. 56) to 343% (Experiment 49 vs. 50), and in the t₂₀₀ values of 108%(Experiment 52 vs. 53) to 312% (Experiment 49 vs. 50).

2.1.3.2.3 Metal Soaps as SCV (Tab. 9-A)

TABLE 9-A Experiment SCV t₁₀ t₅₀ t₂₀₀ TEAP No. Metal soaps [min] [min][min] [phr] 76-A AldiSt ³⁶⁾ [3.2 phr] 11 20 41 — 77-A AldiSt ³⁶⁾ [3.2phr] 21 41 113 0.16 78-A MgSt ³⁷⁾ [3.2 phr] 14 26 65 — 79-A MgSt ³⁷⁾[3.2 phr] 34 54 117 0.16 80-A CaSt ³⁸⁾ [3.2 phr] 24 37 70 — 81-A CaSt³⁸⁾ [3.2 phr] 50 74 151 0.16 82-A Ca/Zn-1 ³⁹⁾ 13 15 26 — 83-A Ca/Zn-1³⁹⁾ 37 43 61 0.16 84 Ca/Zn-2 ⁴⁰⁾ 28 38 74 — 85 Ca/Zn-2 ⁴⁰⁾ 41 51 92 0.16³⁶⁾ Aluminium distearate (from Peter Greven Fettchemie) ³⁷⁾ Magnesiumstearate (from Nitika Chemicals) ³⁸⁾ Calcium stearate (from NitikaChemicals) ³⁹⁾ Bäropan MC 8383 FP (from Bärlocher) ⁴⁰⁾ Astab CZB (fromSun Ace)

As is evident, when commercially available stabilizer systems based oncalcium/zinc soaps (mixed metals) are used, a significant improvement inthe effects is achievable by virtue of addition of TEAP.

2.1.3 Effect of (A) as a PVC Stabilizer (in the Presence of InitialColour Improvers—ICIs)—Tab. 9-B

TABLE 9-B Experiment ICI t₁₀ t₅₀ t₂₀₀ TEAP No. Various [min] [min] [min][phr] 76-B CADMU ⁴⁴⁾ 37 65 162 0.16 77-B CADMU ⁴⁴⁾ 14 25 54 — 78-B DMAU⁴³⁾ 30 58 137 0.16 79-B DMAU ⁴³⁾ 16 25 41 — 80-B AC-1 ⁴¹⁾ 37 64 141 0.1681-B AC-1 ⁴¹⁾ 17 31 55 — 82-B M-DHP-1 ⁴⁶⁾ 46 58 130 0.16 83-B M-DHP-1⁴⁶⁾ 19 41 91 — ⁴¹⁾ 1,4-Butylene glycol bis-3-aminocrotonate (from Lonza)

It is clearly evident that the various initial colour improvers, byvirtue of addition of TEAP, a performance improvement takes place,specifically a rise in the t₁₀, t₅₀ and t₂₀₀ values of 88-164%, 41-160%and 43-200%.

2.1.3.4 Effect of (A) as a PVC Stabilizer (in the Presence of SCV+ICI)2.1.3.4.1 Inorganic (Mineral) Compounds as SCV (Tab. 10)

TABLE 10 Experi- ment t₁₀ t₅₀ t₂₀₀ NaP TEAP No. SCV ICI [min] [min][min] [phr] [phr] 86 CaH (u)⁵⁾ AC-1⁴¹⁾ 46 56 70 — — 87 CaH (u)⁵⁾ AC-1⁴¹⁾119 145 213 — 0.16 88 CaH (u)⁵⁾ AC-2⁴²⁾ 106 131 197 — 0.16 89 CaH (u)⁵⁾DMAU⁴³⁾ 30 37 50 — — 90 CaH (u)⁵⁾ DMAU⁴³⁾ 67 84 122 0.08 — 91 CaH (u)⁵⁾DMAU⁴³⁾ 119 158 260 — 0.16 92 CaH (u)⁵⁾ CADMU⁴⁴⁾ 29 37 50 — — 93 CaH(u)⁵⁾ CADMU⁴⁴⁾ 117 148 226 — 0.16 94 CaH (u)⁵⁾ M-DHP-1⁴⁶⁾ 121 160 265 —0.16 95 CaH (u)⁵⁾ M-DHP-2⁴⁷⁾ 93 146 317 — 0.16 96 CaH (c)⁶⁾ AC-1⁴¹⁾ 5259 71 — — 97 CaH (c)⁶⁾ AC-1⁴¹⁾ 107 126 160 0.08 — 98 CaH (c)⁶⁾ AC-1⁴¹⁾161 188 244 — 0.16 99 CaH (c)⁶⁾ AC-2⁴²⁾ 51 58 68 — — 100 CaH (c)⁶⁾AC-2⁴²⁾ 156 182 238 — 0.16 101 CaH (c)⁶⁾ DMAU⁴³⁾ 34 39 49 — — 102 CaH(c)⁶⁾ DMAU⁴³⁾ 75 90 124 0.08 — 103 CaH (c)⁶⁾ DMAU⁴³⁾ 133 176 283 — 0.16104 CaH (c)⁶⁾ CADMU⁴⁴⁾ 121 155 228 — 0.16 105 CaH (c)⁶⁾ Naf⁴⁵⁾ 52 61 77— — 106 CaH (c)⁶⁾ Naf⁴⁵⁾ 142 218 406 — 0.16 107 CaH (c)⁶⁾ M-DHP-1⁴⁶⁾ 96113 137 — — 108 CaH (c)⁶⁾ M-DHP-1⁴⁶⁾ 135 198 345 — 0.16 109 CaH (c)⁶⁾M-DHP-2⁴⁷⁾ 60 70 84 — — 110 CaH (c)⁶⁾ M-DHP-2⁴⁷⁾ 86 130 262 0.08 — 111CaH (c)⁶⁾ M-DHP-2⁴⁷⁾ 147 217 419 — 0.16 112 Hytal⁷⁾ AC-1⁴¹⁾ 54 60 73 — —113 Hytal⁷⁾ AC-1⁴¹⁾ 136 160 209 — 0.16 114 Hytal⁷⁾ AC-2⁴²⁾ 119 147 200 —0.16 ⁴²⁾Thiodiglycol bis-3-aminocrotonate (from Lonza)⁴³⁾1,3-Dimethyl-6-aminouracile ⁴⁴⁾N-Cyanoacetyl-N,N′-dimethylurea⁴⁵⁾2-Naphthol (ALDRICH) ⁴⁶⁾Monodihydropyridine(1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylic acid dimethylester –Synthesis Example 1.2.1) ⁴⁷⁾Monodihydropyridine (Stavinor ® D507 - fromArkema)

Compared to experiments without ICI and without TEAP (Experiments 5 and6), a positive influence on the thermal stability arises, which ismanifested to a high degree especially in Experiments 91, 94, 121 and100, 103, 106, 108 and 111.

CaH(u) and CaH (c) exhibit, in combination of ICI with TEAP, compared tothe experiments without TEAP (87 vs. 86, 91 vs. 89, 93 vs. 92, 98 vs.96, 100 vs. 99, 103 vs. 101, 106 vs. 105, 108 vs. 107 and 111 vs. 109),a drastic rise in the t₁₀, t₅₀ and t₂₀₀ values by 41-303%, 75-351%, and152-478%. The TEAP combinations exhibit, compared to the sodiumperchlorate combinations (NaP*H₂O) with the same numbers of moles (91vs. 90, 98 vs. 97, 103 vs. 102 and 111 vs. 110), which correspond to thePA, likewise very significant rises in the t₁₀, t₅₀ and t₂₀₀ values,specifically by 50-78%, 49-96% and 53-128%.

In the Hytal system too, combinations of ICI with TEAP exhibit, comparedto the experiments without TEAP (113 vs. 112, 117 vs. 115, 126 vs. 124,129 vs. 127 and 134 vs. 132), a very significant rise in the t₁₀, t₅₀and t₂₀₀ values by 75-152%, 94-167% and 116-255%.

Compared to the possible NaP combinations (117 vs. 116, 119 vs. 118, 126vs. 125, 129 vs. 128 and 134 vs. 133), which correspond to the PA, theTEAP combinations likewise have a significant increase in the t₁₀, t₅₀and t₂₀₀ values, specifically by 16-39%, 16-41% and 14-45%.

In the NaZA system too, combinations of ICI with TEAP, compared toexperiments without TEAP (138 vs. 137, 142 vs. 140, 145 vs. 143 and 149vs. 147), exhibit a very significant rise in the t₁₀, t₅₀ and t₂₀₀values by 75-161%, 61-182 and 185-204%. The TEAP combinations have,compared to the NaP combinations with the same numbers of moles (142 vs.141, 145 vs. 144 and 149 vs. 148), which correspond to the PA, likewisehave a rise in the t₁₀, t₅₀ and t₂₀₀ values, specifically up to 28%, upto 25% and up to 23%.

Here too, the rates of rise in the case of TEAP addition compared toexperiments without TEAP very impressive; the rates of rise compared toNaP addition are considerable.

2.1.3.4.2 Organic Compounds as HCl Scavengers (Tab. 11 and 12)

TABLE 11 Experiment No. SCV Epoxide ICI t₁₀ [min] t₅₀ [min] t₂₀₀ [min]NaP [phr] TEAP [phr] 186 TEPC³²⁾ AC-1⁴¹⁾ 130 140 158 — — 187 TEPC³²⁾AC-1⁴¹⁾ 205 218 256 — 0.16 188 TEPC³²⁾ AC-2⁴²⁾ 137 143 161 — — 189TEPC³²⁾ AC-2⁴²⁾ 196 211 251 — 0.16 190 TEPC³²⁾ DMAU⁴³⁾ 131 137 149 — —191 TEPC³²⁾ DMAU⁴³⁾ 142 157 188 — 0.16 192 TEPC³²⁾ CADMU⁴⁴⁾ 125 132 146— — 193 TEPC³²⁾ CADMU⁴⁴⁾ 147 158 196 0.08 — 194 TEPC³²⁾ CADMU⁴⁴⁾ 169 184222 — 0.16 195 TEPC³²⁾ Naf⁴⁵⁾ 85 97 118 — — 196 TEPC³²⁾ Naf⁴⁵⁾ 161 208308 0.08 — 197 TEPC³²⁾ Naf⁴⁵⁾ 182 216 318 — 0.16 198 TEPC³²⁾ M-DHP-1⁴⁶⁾205 236 329 — 0.16 199 TEPC³²⁾ M-DHP-2⁴⁷⁾ 115 138 175 — — 200 TEPC³²⁾M-DHP-2⁴⁷⁾ 180 224 316 0.08 — 201 TEPC³²⁾ M-DHP-2⁴⁷⁾ 205 241 345 — 0.16202 Hexdge²⁹⁾ AC-1⁴¹⁾ 66 73 86 — — 203 Hexdge²⁹⁾ AC-1⁴¹⁾ 132 148 191 —0.16 204 Hexdge²⁹⁾ AC-2⁴²⁾ 64 71 83 — — 205 Hexdge²⁹⁾ AC-2⁴²⁾ 111 127164 0.08 — 206 Hexdge²⁹⁾ AC-2⁴²⁾ 133 148 182 — 0.16 207 Hexdge²⁹⁾DMAU⁴³⁾ 57 61 69 — — 208 Hexdge²⁹⁾ DMAU⁴³⁾ 125 134 155 — 0.16  208ac-Hexdge^(29a)) DMAU⁴³⁾ 130 140 164 — 0.16 209 Hexdge²⁹⁾ CADMU⁴⁴⁾ 56 5865 — — 210 Hexdge²⁹⁾ CADMU⁴⁴⁾ 119 134 184 0.08 — 211 Hexdge²⁹⁾ CADMU⁴⁴⁾129 143 182 — 0.16 212 Hexdge²⁹⁾ Naf⁴⁵⁾ 96 122 214 — 0.16 213 Hexdge²⁹⁾M-DHP-1⁴⁶⁾ 65 76 92 — — 214 Hexdge²⁹⁾ M-DHP-1⁴⁶⁾ 80 104 176 0.08 — 215Hexdge²⁹⁾ M-DHP-1⁴⁶⁾ 148 173 263 — 0.16 216 Hexdge²⁹⁾ M-DHP-2⁴⁷⁾ 95 121212 — 0.16 217 Glydi³⁰⁾ AC-1⁴¹⁾ 52 74 86 — — 218 Glydi³⁰⁾ AC-1⁴¹⁾ 115133 163 0.08 — 219 Glydi³⁰⁾ AC-1⁴¹⁾ 161 173 204 — 0.16 220 Glydi³⁰⁾AC-2⁴²⁾ 144 158 193 — 0.16 221 Glydi³⁰⁾ DMAU⁴³⁾ 70 73 80 — — 222Glydi³⁰⁾ DMAU⁴³⁾ 115 131 155 0.08 — 223 Glydi³⁰⁾ DMAU⁴³⁾ 128 139 166 —0.16 224 Glydi³⁰⁾ CADMU⁴⁴⁾ 72 75 82 — — 225 Glydi³⁰⁾ CADMU⁴⁴⁾ 130 141167 — 0.16 226 Glydi³⁰⁾ Naf⁴⁵⁾ 88 116 210 — 0.16 227 Glydi³⁰⁾ M-DHP-1⁴⁶⁾64 101 124 — — 228 Glydi³⁰⁾ M-DHP-1⁴⁶⁾ 78 111 182 0.08 — 229 Glydi³⁰⁾M-DHP-1⁴⁶⁾ 140 167 240 — 0.16 230 Glydi³⁰⁾ M-DHP-2⁴⁷⁾ 92 120 200 — 0.16231 DiGlAn⁴⁸⁾ AC-1⁴¹⁾ 98 108 131 — 0.16 232 DiGlAn⁴⁸⁾ AC-2⁴²⁾ 115 119131 — 0.16 233 DiGlAn⁴⁸⁾ DMAU⁴³⁾ 59 62 70 — — 234 DiGlAn⁴⁸⁾ DMAU⁴³⁾ 7986 103 0.08 — 235 DiGlAn⁴⁸⁾ DMAU⁴³⁾ 90 99 121 — 0.16 236 DiGlAn⁴⁸⁾CADMU⁴⁴⁾ 101 110 137 — 0.16 237 DiGlAn⁴⁸⁾ Naf⁴⁵⁾ 97 107 133 — 0.16 238DiGlAn⁴⁸⁾ M-DHP-1⁴⁶⁾ 135 141 152 — 0.16 239 DiGlAn⁴⁸⁾ M-DHP-2⁴⁷⁾ 100 109130 — 0.16 240 TriGlOxAn⁴⁹⁾ AC-1⁴¹⁾ 103 112 133 — 0.16 241 TriGlOxAn⁴⁹⁾AC-2⁴²⁾ 121 125 139 — 0.16 242 TriGlOxAn⁴⁹⁾ DMAU⁴³⁾ 82 85 94 — — 243TriGlOxAn⁴⁹⁾ DMAU⁴³⁾ 104 110 125 0.08 — 244 TriGlOxAn⁴⁹⁾ DMAU⁴³⁾ 116 121135 — 0.16 245 TriGlOxAn⁴⁹⁾ CADMU⁴⁴⁾ 119 125 142 — 0.16 246 TriGlOxAn⁴⁹⁾Naf⁴⁵⁾ 98 105 121 — 0.16 247 TriGlOxAn⁴⁹⁾ M-DHP-1⁴⁶⁾ 116 121 134 — 0.16248 TriGlOxAn⁴⁹⁾ M-DHP-2⁴⁷⁾ 104 110 139 — 0.16 249 BADGE²⁵⁾ AC-1⁴¹⁾ 87140 166 — — 250 BADGE²⁵⁾ AC-1⁴¹⁾ 133 155 193 — 0.16 251 BADGE²⁵⁾ AC-2⁴²⁾125 150 185 — 0.16 252 BADGE²⁵⁾ DMAU⁴³⁾ 56 62 70 — — 253 BADGE²⁵⁾DMAU⁴³⁾ 132 143 164 — 0.16 254 BADGE²⁵⁾ CADMU⁴⁴⁾ 124 156 186 — 0.16 255BADGE²⁵⁾ Naf⁴⁵⁾ 46 84 202 — 0.16 256 BADGE²⁵⁾ M-DHP-1⁴⁶⁾ 89 142 323 —0.16 257 BADGE²⁵⁾ M-DHP-2⁴⁷⁾ 48 88 201 — 0.16 258 BFDGE²⁶⁾ AC-1⁴¹⁾ 61112 131 — — 259 BFDGE²⁶⁾ AC-1⁴¹⁾ 91 132 175 0.08 — 260 BFDGE²⁶⁾ AC-1⁴¹⁾154 166 193 — 0.16 261 BFDGE²⁶⁾ AC-2⁴²⁾ 145 158 191 — 0.16 262 BFDGE²⁶⁾DMAU⁴³⁾ 63 67 74 — — 263 BFDGE²⁶⁾ DMAU⁴³⁾ 105 136 156 0.08 — 264BFDGE²⁶⁾ DMAU⁴³⁾ 128 140 164 — 0.16 265 BFDGE²⁶⁾ CADMU⁴⁴⁾ 121 146 175 —0.16 266 BFDGE²⁶⁾ Naf⁴⁵⁾ 49 86 199 — 0.16 267 BFDGE²⁶⁾ M-DHP-1⁴⁶⁾ 77 125217 — 0.16 268 BFDGE²⁶⁾ M-DHP-2⁴⁷⁾ 48 88 194 — 0.16 269 Epikote828²⁷⁾AC-1⁴¹⁾ 102 145 211 — 0.16 270 Epikote828²⁷⁾ AC-2⁴²⁾ 118 153 203 — 0.16271 Epikote828²⁷⁾ DMAU⁴³⁾ 122 150 175 — 0.16 272 Epikote828²⁷⁾ CADMU⁴⁴⁾54 60 67 — — 273 Epikote828²⁷⁾ CADMU⁴⁴⁾ 89 126 174 — 0.16 274Epikote828²⁷⁾ Naf⁴⁵⁾ 53 103 248 — 0.16 275 Epikote828²⁷⁾ M-DHP-1⁴⁶⁾ 4068 157 — 0.16 276 Epikote828²⁷⁾ M-DHP-2⁴⁷⁾ 56 101 218 — 0.16 277Epikote1002²⁸⁾ AC-1⁴¹⁾ 19 36 59 — — 278 Epikote1002²⁸⁾ AC-1⁴¹⁾ 56 77 145— 0.16 279 Epikote1002²⁸⁾ AC-2⁴²⁾ 16 38 68 — — 280 Epikote1002²⁸⁾AC-2⁴²⁾ 60 79 133 — 0.16 281 Epikote1002²⁸⁾ DMAU⁴³⁾ 16 29 45 — — 282Epikote1002²⁸⁾ DMAU⁴³⁾ 44 76 142 — 0.16 283 Epikote1002²⁸⁾ CADMU⁴⁴⁾ 2031 49 — — 284 Epikote1002²⁸⁾ CADMU⁴⁴⁾ 52 85 153 — 0.16 285Epikote1002²⁸⁾ Naf⁴⁵⁾ 19 31 55 — — 286 Epikote1002²⁸⁾ Naf⁴⁵⁾ 26 50 139 —0.16 287 Epikote1002²⁸⁾ M-DHP-1⁴⁶⁾ 22 46 100 — — 288 Epikote1002²⁸⁾M-DHP-1⁴⁶⁾ 32 55 140 — 0.16 289 Epikote1002²⁸⁾ M-DHP-2⁴⁷⁾ 20 38 74 — —290 Epikote1002²⁸⁾ M-DHP-2⁴⁷⁾ 42 73 181 — 0.16⁴⁸⁾N,N-Diglycidylaniline(ALDRICH)⁴⁹⁾N,N-Diglycidyl-4-glycidyloxyaniline(ALDRICH)

Here too, the rates of rise are present (201 vs. 199 and 201 vs. 200);they are 78%, 75% and 97% for the t₁₀, t₅₀ and t₂₀₀ values, and 14% t₁₀value.

Here, likewise significant rates of rise are present (206 vs. 204 and215 vs. 213) with values of 108-128%, 108-128% and 119-197%, and also,for 206 vs. 205 and 215 vs. 214, with values of 20-88%, 17-66% and11-49%.

Here, the rates of rise (219 vs. 217, 223 vs. 221 and 229 vs. 227 and219 vs. 218, 223 vs. 222 and 229 vs. 228) are with rates of rise of83-210%, 65-134% and 94-137%, and also up to 79%, up to 50% and up to32%.

Here, the rates of rise (235 vs. 233 and 244 vs. 242 and 235 vs. 234 and244 vs. 243) are 41-53%, 42-40% and 44-73%, and also up to 14%, up to15% and up to 17%.

Here (260 vs. 258 and 264 vs. 262, and also 260 vs. 259 and 264 vs.263), the rates of rise are 103-152%, 48-109% and 47-122%, and also upto 69%, up to 35% and up to 10%.

From this illustration too, the positive effect in the case ofadditional TEAP addition on the t₁₀ value is particularly evident (273vs. 272, 278 vs. 277, 280 vs. 279, 282 vs. 281, 284 vs. 283 and 290 vs.289).

Here (293 vs. 291, 297 vs. 295, 300 vs. 298, 303 vs. 301 and 306 vs.304, and also 293 vs. 292, 297 vs. 296, 300 vs. 299, 303 vs. 302 and 306vs. 305), the rates of rise are 51-81%, 53-79% and 68-99%, and also14-40%, 15-39% and 20-39%.

TABLE 12 Experiment SCV t_(ind.) ⁵⁰⁾ t₅₀ t₂₀₀ NaP TEAP No. Cyanamide ICI[min] [min] [min] [phr] [phr] 291 Didi-f ²⁰⁾ AC-1 ⁴¹⁾ 75 78 87 — — 292Didi-f ²⁰⁾ AC-1 ⁴¹⁾ 86 91 108 0.08 — 293 Didi-f ²⁰⁾ AC-1 ⁴¹⁾ 113 119 146— 0.16 294 Didi-f ²⁰⁾ AC-2 ⁴²⁾ 113 119 145 — 0.16 295 Didi-f ²⁰⁾ DMAU⁴³⁾ 69 73 80 — — 296 Didi-f ²⁰⁾ DMAU ⁴³⁾ 102 107 128 0.08 — 297 Didi-f²⁰⁾ DMAU ⁴³⁾ 125 131 159 — 0.16 298 Didi-f ²⁰⁾ CADMU ⁴⁴⁾ 70 74 81 — —299 Didi-f ²⁰⁾ CADMU ⁴⁴⁾ 82 89 111 0.08 — 300 Didi-f ²⁰⁾ CADMU ⁴⁴⁾ 115124 154 — 0.16 301 Didi-f ²⁰⁾ Naf ⁴⁵⁾ 68 74 89 — — 302 Didi-f ²⁰⁾ Naf⁴⁵⁾ 98 111 143 0.08 — 303 Didi-f ²⁰⁾ Naf ⁴⁵⁾ 112 128 172 — 0.16 304Didi-f ²⁰⁾ M-DHP-1 ⁴⁶⁾ 83 86 95 — — 305 Didi-f ²⁰⁾ M-DHP-1 ⁴⁶⁾ 107 118145 0.08 — 306 Didi-f ²⁰⁾ M-DHP-1 ⁴⁶⁾ 126 142 185 — 0.16 307 Didi-f ²⁰⁾M-DHP-2 ⁴⁷⁾ 129 142 180 — 0.16 308 Mel-f ²³⁾ AC-1 ⁴¹⁾ 68 71 80 — — 309Mel-f ²³⁾ AC-1 ⁴¹⁾ 124 133 157 0.08 — 310 Mel-f ²³⁾ AC-1 ⁴¹⁾ 142 154 184— 0.16 311 Mel-f ²³⁾ AC-2 ⁴²⁾ 134 150 187 — 0.16 312 Mel-f ²³⁾ DMAU ⁴³⁾67 70 76 — — 313 Mel-f ²³⁾ DMAU ⁴³⁾ 80 112 129 0.08 — 314 Mel-f ²³⁾ DMAU⁴³⁾ 136 149 169 — 0.16 315 Mel-f ²³⁾ CADMU ⁴⁴⁾ 58 62 76 — — 316 Mel-f²³⁾ CADMU ⁴⁴⁾ 100 115 148 0.08 — 317 Mel-f ²³⁾ CADMU ⁴⁴⁾ 159 168 202 —0.16 ⁵⁰⁾ Induction time

Here (310 vs. 308, 314 vs. 312, 317 vs. 315, 320 vs. 318, 323 vs. 312and 326 vs. 324, and also 310 vs. 309, 314 vs. 313, 317 vs. 316, 320 vs.319, 323 vs. 322 and 326 vs. 325), the rates of rise are 101-174%,113-171% and 122-231%, and also 11-70%, 9-46% and 10-36%.

2.1.3.4.3 Other IC Improvers as Cocomponent (Tab. 13)

TABLE 13 Experiment SCV t_(i10) t₅₀ t₂₀₀ TEAP No. CaH/Mel ICI [min][min] [min] [phr] 327 CaH (c) ⁶⁾ B-DHP ⁵²⁾ 129 171 277 0.16 328 CaH (c)⁶⁾ B-t-DHP ⁵³⁾ 109 138 225 0.16 329 CaH (c) ⁶⁾ P-DHP ⁵⁴⁾ 148 204 3340.16 330 CaH (c) ⁶⁾ P-t-DHP ⁵⁵⁾ 122 164 273 0.16 331 Mel-f ²³⁾ B-DHP ⁵²⁾119 146 212 0.16 332 Mel-f ²³⁾ B-t-DHP ⁵³⁾ 111 138 213 0.16 333 Mel-f²³⁾ P-DHP ⁵⁴⁾ 138 161 229 0.16 334 TEPC ³²⁾ Hyd ⁵⁶⁾ 124 145 218 0.16 335CaH (c) ⁶⁾ Hyd ⁵⁶⁾ 129 188 344 0.16 336 Hytal ⁷⁾ Hyd ⁵⁶⁾ 101 137 2440.16 337 Hexdge ²⁹⁾ Hyd ⁵⁶⁾ 83 112 209 0.16 338 NaZA ¹⁰⁾ Hyd ⁵⁶⁾ 85 89193 0.16 339 BADGE ²⁵⁾ Hyd ⁵⁶⁾ 35 66 172 0.16 340 BFDGE ²⁶⁾ Hyd ⁵⁶⁾ 3971 178 0.16 ⁵²⁾ Bisdihydropyridine(bis[1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylic acid]1,4-butanediol diester - Synthesis Example 1.2.2) ⁵³⁾ Bisdihydropyridine(bis[1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylic acid]thiodiethylene glycol diester - Synthesis Example 1.2.3) ⁵⁴⁾Polydihydropyridine(poly[1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylic acid]1,4-butanediol ester - Synthesis Example 1.2.4) ⁵⁵⁾ Polydihydropyridine(poly[1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylic acid]thiodiethylene glycol ester] - Synthesis Example 1.2.5) ⁵⁶⁾ Hydantoin(ALDRICH)

Here too, it is evident that good effects are achievable.

2.2 Performance of the Static Heat Test (SHT) 2.2.1 Production of theRolled Sheets

100 parts of the dry mixtures made up according to the followingcomposition are plastified at 180° C. with addition of 0.5-0.8 part⁵⁷)of a paraffin-based lubricant on a Collin laboratory analysis rollmill⁵⁸), in each case for 5 minutes. The films thus obtained (thickness0.3 mm) are sent to further measurements.

100.0 parts of Vinnolit S3160 (PVC K value=60)

0.4 part of initial colour improver (ICI)

1.6 parts of HCl scavenger (SCV)

0.16 part of TEAP (Comp. A)

2.2.2 Performance of the Examination

Test strips (16 mm×300 mm) are cut out of the rolled sheets producedaccording to Example 2.2.1. They are stressed at 180° C. until theydarken in colour (burn) in a Mathis thermotester (LTE type; feed: 5 mm,base time 5 or 45 min, cycle time 5 min). Thereafter, the YI (yellownessindex) is determined to DIN 53381¹²) and compared to the YI of theunstressed rolled sheet (zero minute value). The results of a fewrepresentatives are compiled in Tab. 14. The higher the YI, the yellower(darker) the sample. The lower the YI, the lighter the sample and thebetter the result.

2.2.3 Examples (Yellowness Indices—YI, Tab. 14)

TABLE 14 Mono- DMAU DHP-1 (ICI) (ICI) Example No. 2.2.3.1 2.2.3.22.2.3.3 2.2.3.4 2.2.3.5 2.2.3.6 CaH(c) NaZA Mel NaZA Mel CaH(c) (SCV) +(SCV) + (SCV) + (SCV) + (SCV) + (SCV) + Minutes TEAP TEAP TEAP NaP NaPTEAP 0 n.d. n.d. n.d. n.d. n.d. n.d. 10 6.6 7.9 5.7 19.5 17.9 6.6 20 7.711.1 8.3 32.3 24.8 7.6 30 10.0 15.0 13.1 44.8 37.3 9.7 40 15.2 19.9 23.053.6 48.9 16.3 50 23.6 28.4 33.9 59.0 57.6 25.4 60 34.7 35.2 46.8 63.564.1 46.8 70 50.4 41.3 57.7 71.4 72.8 75.0 80 66.4 48.4 71.4 78.7 84.782.5 90 85.5 54.8 86.7 90.2 102.0 100

It is clearly evident that the overall performance can be vastlyimproved by adding TEAP (comp. A) instead of NaP. For instance, therises in the case of the NaZA/DMAU/TEAP vs. NaZA/DMAU/NaP system (2 vs.4) are an initial improvement in colour (ICI—10 min) of 147%, animprovement in the colour retention (CR—30 min) of 199% and an increasein the long-term stability (LTS—60 min) of 80%.

For the alternative Mel/DMAU/TEAP vs. NaZA/DMAU/NaP system (3 vs. 4),the improvements are 242% for the IC (10 min), 242% for the CR (30 min),and 36% for the LT (60 min).

In the case of the CaH (c)/DMAU/TEAP vs. NaZA/DMAU/NaP system (1 vs. 4),the rates of rise are 195% for the IC (10 min), 348% for the CR (30min), and 87% for the LT (60 min).

For the likewise alternative CaH(c)/Mono-DHP-1/TEAP vs. NaZA/DMAU/NaPsystem (6 vs. 4), increases of 195% for the IC (10 min), of 362% for theCR (30 min), and of 37% for the LT (60 min) are recorded.

A drastic improvement in the performance is found.

1. Composition comprising at least one synthetic polymer and at leastone coordination-polymeric triethanolamineperchlorato(triflato)metalinner complex comprising the monomer unit of the formula (A):

where Mt=Li, Na, K, Mg, Ca, Sr, Ba and Zn; An=OClO₃ or OS(O₂)CF₃; q=1 or2.
 2. Composition according to claim 1, characterized in that thesynthetic polymer is a halogenated polymer, preferably PVC. 3.Stabilizer system for synthetic polymers, comprising acoordination-polymeric triethanolamineperchlorato(triflato)metal innercomplex comprising the monomer unit of the formula (A):

where Mt=Li, Na, K, Mg, Ca, Sr, Ba and Zn; An=OClO₃ or OS(O₂)CF₃; q=1 or2.
 4. Stabilizer system according to claim 3, characterized in thatadditionally present is a linear and cyclic ureide (substitutedcyanoacetylurea, substituted iminobarbituric acid, substitutedaminouracil, hydantoin) and/or a 3-aminocrotonic ester and/or adihydropyridinedicarboxylic ester of the formula (B-1), (B-2), (C-1) and(C-2)

and

and

where X=O or S; Y=CH₂CN, Z=H, or Y and Z form the bridging memberCH₂—C═NH, CR⁵═C—NHR⁶ or R¹R²C. R¹, R² are each independently H,C₁-C₂₂-alkyl, cyclohexyl, (meth)allyl, oleyl, phenyl, benzyl, phenethyl,(tetrahydro)naphthyl, meth (or eth)oxypropyl (or ethyl),CH₂—CHOH—R^(1a), CH₂—CHOH—CH₂X′R^(1a); X′=O or S; R^(1a)=H, C₁₋₂₂-alkyl,cyclohexyl, (meth)allyl, oleyl, phenyl, benzyl, phenethyl,(tetrahydro)naphthyl or meth (or eth)oxypropyl (or ethyl); R³=unbranchedor branched C₂-C₂₀-alkylene which may be interrupted by 1 to 4 oxygen orsulphur atoms and/or may be substituted by 1 to 4 OH groups, ordimethylolcyclohexane-1,4-diyl, polyethylene (or-propylene)glycol-α,ω-diyl (preferably, poly=tetra to deca),polyglyceryl-α,ω-diyl (preferably, poly=tetra to deca) or glyceroltriyl,trimethylolethane (or -propane)triyl, pentaerythritoltri (or -tetra)yl,bis(trimethylolethane (or -propane)tri (or -tetra)yl), diglyceroltri (or-tetra)yl, tetritoltetrayl, triglyceroltri (or -tetra, -penta)yl,pentitolpentayl, dipentaerythritolpenta (or -hexa)yl and hexitolhexayl;n=2, 3, 4, 5 or 6; R⁵=H or (C₃-C₁₀-alkylidene)_(1/2); where thisalkylidene may be interrupted by up to 2 oxygen atoms or may have up to2 substituents selected independently from the group consisting of OH,phenyl and hydroxyphenyl; R⁶=H, hydroxy-C₂-C₄-alkyl,3-C₁-C₁₀-alkoxy-2-hydroxypropyl, or mono- to trihydroxy-, mono- totri-C₁-C₄-alkyl- or/and mono- to tri-C₁-C₄-alkoxyphenyl, allyl, mono- totrisubstituted phenyl; R⁷, R^(7′) are each independently branched andunbranched C₁-C₄-alkyl, phenyl, cyclohexyl; W=CO₂CH₃, CO₂C₂H₅, CO₂^(n)C₁₂H₂₅ or CO₂C₂H₄—S—^(n)C₁₂H₂₅; L, T=unsubstituted C₁₋₁₂-alkyl; andm and n′ are each integers of 0 to 20, k is 0 or 1 and R and R′ are eachindependently ethylene, propylene, butylene or an alkylene- orcycloalkylenebismethylene group of the—(C_(p)H_(2p)—X″—)_(t)C_(p)H_(2p)— type where p is an integer of 2 to 8,t is an integer of 0 to 10 and X″ is oxygen or sulphur.
 5. Stabilizersystem according to claim 3 or 4, characterized in that additionallyadded is magnesium oxide or calcium oxide or magnesium hydroxide orcalcium hydroxide and/or a magnesium soap or calcium soap and/or a Ca/Znstabilizer and/or an (optionally Li- or titanium-containing)hydrotalcite and/or dawsonite and/or sodium zeolite A and/or a calciumaluminium hydroxo hydrogenphosphite and/or a glycidyl compound and/or anepoxidized fatty acid ester and/or a melamine and/or a phosphorous esterand/or 2-naphthol and/or a cyanamide of the formula (E)

where each R₄ is independently H, nitrile, carbamoyl, R¹, R², R¹CO,R²CO, Na, K, Mg_(1/2) and Ca_(1/2), or R₂ ⁴=tetra-, penta- orhexamethylene, and o=1, 2 or
 3. 6. Stabilizer system according to one ofclaims 3 to 5, characterized in that a sterically hindered amine (HALS)and/or an antioxidant and/or a UV absorber (benzotriazole derivative)and/or titanium dioxide and/or chalk is added.
 7. Stabilizer systemaccording to claim 6, characterized in that the sterically hinderedamine (HALS) is an NOR-HALS compound.
 8. Stabilizer system according toclaim 7, characterized in that the NOR-HALS compound is a triazine-basedNOR-HALS compound.
 9. Stabilizer system according to any of claims 3 to8, characterized in that it further comprises a glyceryl ether and/orester, R⁸OCH₂CH(OH)CH₂OH or R⁸CO₂CH₂CH(OH)CH₂OH and/or a DEA derivativeR⁹—[C(O)]_(d)—N(C₂H₄OH)₂ or R⁸OCH₂CH(OH)CH₂—[C(O)]_(d)—N(C₂H₄OH)₂ orR⁹—N(OH)(CH₂)₂(CH₂)₃—[C(O)]_(d)—N(C₂H₄OH)₂ and/or a paraffinsulphate (or-sulphonate) salt C₁₂-C₁₈-alkyl-(O)_(d′)—SO₃ Na, Li, K and/or apolyoxyalkylene of the formula (F)R⁸—O—[CH(R¹⁰)—CH₂—O—]_(a)—[CH₂—[CH(OH)]_(b)—CH₂—O]_(c)[C(O)]_(d″)—R⁹  (F)where each R⁸ is independently H, C₁-C₂₄-alkyl, C₂-C₂₄-alkenyl,CH₂═CH—C(O) or CH₂═CCH₃—C(O); each R⁹ is independently C₁-C₂₄-alkyl,C₂-C₂₄-alkenyl, (CH₂)₂OH, CH₂—COOH or N(C₁-C₈-alkyl)₃Hal, R¹⁰=H or CH₃,Hal=Cl, Br or I; a=an integer greater than or equal to 2, b=an integerof 1 to 6, and c, d, d′, d″ are each independently 0 or
 1. 10.Composition comprising a synthetic polymer and a stabilizer systemaccording to any of claims 4 to
 9. 11. Composition according to claim10, characterized in that the synthetic polymer is a chlorinatedpolymer, preferably PVC.
 12. Composition according to claim 11,characterized in that the chlorinated polymer is rigid PVC, flexiblePVC, suspension PVC or emulsion PVC.
 13. Composition according to any ofclaims 10 to 12, characterized in that, based on 100 parts by weight ofsynthetic polymer, 0.001-1.0 part by weight of the inner complex (A) ispresent.
 14. Composition according to any of claims 10 to 13,characterized in that 0.01-10 parts by weight of sterically hinderedamine and/or NOR-HALS compound and/or UV absorber and/or titaniumdioxide are present.
 15. Composition according to any of claims 10 to14, characterized in that the synthetic polymer is flexible PVC and thestabilizer system comprises 1,4-cyclohexanedimethanol diglycidyl ether.16. Process for stabilizing synthetic polymers by adding a stabilizersystem according to any of claims 5 to 10 to a synthetic polymer. 17.Process for stabilizing synthetic polymers according to claim 16,characterized in that the synthetic polymer is a chlorinated polymer,preferably flexible PVC or PVC paste.
 18. Process for stabilizingchlorinated polymers according to claim 17, characterized in that theflexible PVC is suitable for the manufacture of floors, motor vehicleparts, wallpaper, flexible films, pipes, injection mouldings orpreferably for wire sheathing (cables).
 19. Process for stabilizingsynthetic polymers according to claim 17, characterized in that thechlorinated polymer is rigid PVC.
 20. Process for stabilizingchlorinated polymers according to claim 19, characterized in that therigid PVC is suitable for the production of films (including Luvitherm),PVC pipes or profiles, preferably of window profiles.
 21. Usefularticles comprising PVC, which also comprise a stabilizer systemaccording to any of claims 5 to
 10. 22. Antistat or antistat componentfor synthetic polymers, comprising atriethanolamineperchlorato(triflato)metal inner complex of the formula(A) as specified in claim
 1. 23. Inner complex of the formula (A) asspecified in claim 1, characterized in that Mt═Ca or Zn and q=2. 24.Inner complex of the formula (A) as specified in claim 1, where Mt=Li,Na or Ca and q=1 or
 2. 25. Inner complexes according to claim 24,characterized in that Mt═Li or Na, q=1 and An=OClO₃.
 26. Process forpreparing an inner complex of the formula (A) as specified in claim 1,characterized in that the synthesis is effected in methanol, ethanol,propanol, triethanolamine or water, and the solvent and any water ofreaction are removed by distillation.
 27. Process according to claim 26,characterized in that the distillation residue is digested in a nonpolarsolvent.
 28. Process for preparing inner complexes of the formula (A) asspecified in claim 1, characterized in that the synthesis is effected inan alcohol and the reaction product is removed by precipitation with anonpolar solvent.